JP6650507B2 - Antireflection film and method of manufacturing antireflection film - Google Patents

Description

  The present invention relates to an antireflection film and a method for manufacturing the antireflection film.

  Image displays such as cathode ray tube displays (CRTs), plasma displays (PDPs), electroluminescent displays (ELDs), fluorescent displays (VFDs), field emission displays (FEDs), and liquid crystal displays (LCDs) An anti-reflection film may be provided in order to prevent a decrease in contrast or reflection of an image due to reflection of external light on the display surface. Further, an anti-reflection film may be provided with an anti-reflection function even in a device other than the image display device such as a glass surface of a show room.

  As an antireflection film used by being disposed on the front surface of a display, Patent Document 1 has at least three or more reactive groups in one molecule which can be polymerized by irradiation with active energy rays, and polydimethylsiloxane; An antireflection film containing a polyorganosiloxane in which a diisocyanate or a triisocyanate and a polyester having a polymerizable reactive group are formed into a urethane bond is described.

  In addition, plastic molded products are generally coated with a coating film from the viewpoint of protecting the surface from damage, etc., and Patent Document 2 discloses that a polysiloxane site and five or more polysiloxane moieties are contained in one molecule. A curable resin composition comprising a (meth) acrylate compound having a specific structure having a (meth) acryloyloxy group, a urethane (meth) acrylate, and a photopolymerization initiator is described.

  On the other hand, as an anti-reflection film, an anti-reflection film having a fine uneven shape having a period equal to or less than the wavelength of visible light on a substrate surface, that is, an anti-reflection film having a so-called moth eye structure is known. The moth-eye structure can create a refractive index gradient layer in which the refractive index changes continuously from the air toward the bulk material inside the base material for visible light, and can prevent light reflection.

  As an antireflection film having a moth-eye structure, Patent Literature 3 discloses that a coating solution containing a transparent resin monomer and fine particles is applied on a transparent base material, cured to form a transparent resin in which fine particles are dispersed, and then the transparent resin is formed. An antireflection film having a moth-eye structure manufactured by etching a resin is described.

Japanese Patent No. 5055763 Japanese Patent No. 5625931 Japanese Patent Application Laid-Open No. 2009-139796

  However, with the spread of thin and lightweight displays typified by liquid crystal displays (LCDs) and organic EL displays (OLEDs), articles, situations, and usage forms of the displays are becoming wider and more complex. In the techniques of Patent Documents 1 to 3, required abrasion resistance (mainly rubbing of steel wool) is still insufficient, and it is necessary to further improve performance. Further, the antireflection performance is not sufficient at the level described in Patent Document 1.

  An object of the present invention is to provide an antireflection film having good antireflection performance, a small change in reflectance before and after a scratch resistance test, and excellent practical scratch resistance, and the antireflection film. To provide a method for easily producing

  The present inventors have studied diligently, and in order to solve the above-mentioned problems, it is important that the anti-reflection layer, particularly forming an extremely shallow region of the surface, has both the cross-linking group density and the slipperiness of the material itself. I came to the conclusion. In particular, the case where the antireflection layer has a moth-eye structure having an uneven shape on the surface is remarkable. Conventional slip agents focus only on the slipperiness, and the density of the cross-linking group of the material itself is not high, so even if it exists on the outermost surface of the convex part of the moth-eye structure, it works effectively at the beginning of the scratch resistance test. , Are immediately cut off, cannot maintain the slipperiness, and damage the antireflection layer. On the other hand, by using a specific material having a high crosslinking group density and a slippery property, a coating having a high crosslinkage density and a slippery property is formed on the outermost surface of the convex portion of the moth-eye structure. It has been found that it is possible to withstand a load concentrated on the convex portion at the time of the abrasion resistance test to be rubbed, to maintain the irregular shape, and to prevent scratching. That is, it has been found that the above-mentioned problems can be solved by the following means.

一般式（Ｐ）中、Ｒｐ ^１ 及びＲｐ ^２ はそれぞれ独立に、水素原子、一価の炭化水素基、アルコキシ基、又はアリーロキシ基を表す。ｎは２以上の整数を表す。

一般式（Ｍ−１）中、Ｒ _１ は水素原子、アルキル基、アルケニル基、アルキルオキシ基、アルケニルオキシ基、アルキルオキシアルキル基、又はアルケニルオキシアルキル基を表す。Ｒ _１１ 及びＲ _１２ は各々独立に水素原子又はメチル基を表す。＊は結合位置を表す。
一般式（Ｍ−２）中、Ｒ _２１ 〜Ｒ _２３ は各々独立に水素原子又はメチル基を表す。＊は結合位置を表す。
一般式（Ｍ−３）中、Ｒ _３１ 〜Ｒ _３５ は各々独立に水素原子又はメチル基を表す。＊は結合位置を表す。
〔２〕
上記反射防止層の上記基材側の面とは反対側の最表面を、荷重２００ｇの条件でスチールウールで１０往復擦った後の上記反射防止フィルムの反射率をＲ _Ａ 、スチールウールで擦る前の上記反射防止フィルムの反射率をＲ _０ としたとき、Ｒ _Ａ −Ｒ _０ で表される反射率変化が０．２５％以下である、〔１〕に記載の反射防止フィルム。
〔３〕
上記滑り剤（ａ）の上記架橋基が（メタ）アクリロイル基である、〔１〕又は〔２〕に記載の反射防止フィルム。
〔４〕
上記滑り剤（ａ）の上記フッ素原子及びシロキサン結合の少なくとも一種を含む部位は、ポリジメチルシロキサン基又はポリエーテル変性ジメチルシロキサン基である、〔１〕〜〔３〕のいずれか１項に記載の反射防止フィルム。
〔５〕
上記滑り剤（ａ）が上記化合物（ａ１）であって、上記化合物（ａ１）は、上記架橋基がＣ−Ｃ結合又はＣ−Ｏ結合で主鎖に連結している、〔１〕〜〔４〕のいずれか１項に記載の反射防止フィルム。
〔６〕
上記滑り剤（ａ）が上記化合物（ａ２）であって、上記化合物（ａ２）は、上記フッ素原子及びシロキサン結合の少なくとも一種を含む部位と、上記架橋基とがＣ−Ｃ結合又はＣ−Ｏ結合を介して結合している、〔１〕〜〔４〕のいずれか１項に記載の反射防止フィルム。
〔７〕
上記反射防止層は、平均一次粒径が２５０ｎｍ以下の粒子（ｄ）を有する、〔１〕〜〔６〕のいずれか１項に記載の反射防止フィルム。
〔８〕
上記反射防止層の上記基材側とは反対側の表面に上記粒子（ｄ）によって形成された凹凸形状を有する、〔７〕に記載の反射防止フィルム。
〔９〕
上記基材の可視光の透過率が８０％以上である、〔１〕〜〔８〕のいずれか１項に記載の反射防止フィルム。
〔１０〕
上記反射防止層には、上記基材の表面に直交する方向に上記粒子（ｄ）が複数存在しない、〔８〕に記載の反射防止フィルム。
〔１１〕
〔８〕に記載の反射防止フィルムの製造方法であって、
上記基材上に、
上記滑り剤（ａ）、上記硬化性化合物（ｂ）、上記光重合開始剤（ｃ）、上記粒子（ｄ）、及び溶剤を含む組成物を塗布し、上記溶剤を揮発させ、上記粒子（ｄ）が存在しない部分の厚みが上記粒子（ｄ）の平均一次粒径の０．８倍以上の厚さとなる層（Ａ）を設ける工程（１）と、
上記層（Ａ）中の上記硬化性化合物（ｂ）の一部を硬化させ、硬化された化合物（ｂｃ）を得る工程（２）と、
上記層（Ａ）中の上記硬化性化合物（ｂ）及び上記化合物（ｂｃ）からなる群より選択される化合物の一部を、加熱により上記基材に浸透させるか又は揮発させ、上記層（Ａ）の上記基材側とは反対の最表面に上記粒子（ｄ）からなる凹凸形状を形成する工程（３）と、
上記層（Ａ）中に残存する、上記滑り剤（ａ）、上記硬化性化合物（ｂ）及び上記化合物（ｂｃ）からなる群より選択される化合物を硬化させて、上記反射防止層を形成する工程（４）と、
をこの順に有する、反射防止フィルムの製造方法。
〔１２〕
上記工程（１）と上記工程（２）の間、上記工程（２）と上記工程（３）の間、又は上記工程（３）と上記工程（４）の間に、
上記硬化性化合物（ｂ）とは相溶しない化合物（ｅ）を含む層（Ｅ）を、上記層（Ａ）の上記基材側の面とは反対側の面上に設ける工程（Ｅ１）を有し、
上記工程（Ｅ１）に引き続いて行う上記工程（２）、上記工程（３）又は上記工程（４）の後に、上記層（Ｅ）を除去する工程（Ｅ２）を有する、〔１１〕に記載の反射防止フィルムの製造方法。
本発明は、上記〔１〕〜〔１２〕に係る発明であるが、以下、それ以外の事項についても参考のため記載している。
＜１＞
基材上に、少なくとも１層の反射防止層を有し、
上記反射防止層は、上記基材側の面とは反対側の最表面から上記基材に向かう方向に２０ｎｍ以下の厚みの領域（Ｓ）内に、
１分子中に架橋基を３つ以上持ち、架橋基当量が４５０以下であり、フッ素原子及びシロキサン結合の少なくとも一種を含む部位を有する滑り剤（ａ）と、
少なくとも１分子中に架橋基を３つ以上持ち、架橋基当量が４５０以下であり、フッ素原子及びシロキサン結合のいずれも有さない硬化性化合物（ｂ）と、
光重合開始剤（ｃ）と、を含む硬化性組成物の硬化物を含み、
上記領域（Ｓ）の断面方向の素材分布において、上記滑り剤（ａ）の含有率が５１％以上となる領域を有する、反射防止フィルム。
＜２＞
上記反射防止層の上記基材側の面とは反対側の最表面を、荷重２００ｇの条件でスチールウールで１０往復擦った後の上記反射防止フィルムの反射率をＲ_Ａ、スチールウールで擦る前の上記反射防止フィルムの反射率をＲ_０としたとき、Ｒ_Ａ−Ｒ_０で表される反射率変化が０．２５％以下である、＜１＞に記載の反射防止フィルム。
＜３＞
上記滑り剤（ａ）の上記架橋基が（メタ）アクリロイル基である、＜１＞又は＜２＞に記載の反射防止フィルム。
＜４＞
上記滑り剤（ａ）の上記フッ素原子及びシロキサン結合の少なくとも一種を含む部位は、フルオロアルキル基である、＜１＞〜＜３＞のいずれか１項に記載の反射防止フィルム。
＜５＞
上記滑り剤（ａ）の上記フッ素原子及びシロキサン結合の少なくとも一種を含む部位は、ポリジメチルシロキサン基又はポリエーテル変性ジメチルシロキサン基である、＜１＞〜＜３＞のいずれか１項に記載の反射防止フィルム。
＜６＞
上記滑り剤（ａ）は、側鎖に上記フッ素原子及びシロキサン結合の少なくとも一種を含む部位と上記架橋基を持ち、重量平均分子量が６，０００以上である化合物（ａ１）である、＜４＞又は＜５＞に記載の反射防止フィルム。
＜７＞
上記化合物（ａ１）は、上記架橋基がＣ−Ｃ結合又はＣ−Ｏ結合で主鎖に連結している、＜６＞に記載の反射防止フィルム。
＜８＞
上記滑り剤（ａ）は、上記フッ素原子及びシロキサン結合の少なくとも一種を含む部位に、上記架橋基が直接又は連結基を介して結合した、重量平均分子量が６，０００未満である化合物（ａ２）である、＜４＞又は＜５＞に記載の反射防止フィルム。
＜９＞
上記化合物（ａ２）は、
下記一般式（Ｍ−２）で表される基を１つ有する化合物、
下記一般式（Ｍ−３）で表される基を１つ有する化合物、
下記一般式（Ｍ−１）で表される基を２つ有する化合物、
下記一般式（Ｍ−２）で表される基を２つ有する化合物、又は、
下記一般式（Ｍ−３）で表される基を２つ有する化合物である、＜８＞に記載の反射防止フィルム。 [1]
On the substrate, has at least one antireflection layer,
The antireflection layer has a thickness (S) of 20 nm or less in a direction from the outermost surface on the opposite side to the surface on the substrate side toward the substrate,
A slip agent (a) having three or more cross-linking groups in one molecule, having a cross-linking group equivalent of 450 or less, and having a site containing at least one of a fluorine atom and a siloxane bond;
A curable compound (b) having at least three crosslinking groups in one molecule, having a crosslinking group equivalent of 450 or less, and having neither a fluorine atom nor a siloxane bond;
A photopolymerization initiator (c), and a cured product of a curable composition containing:
The compound (a1) having a site containing at least one of the fluorine atom and the siloxane bond in the side chain and the crosslinking group, and having a weight average molecular weight of 6,000 or more, or the fluorine atom (a). And a compound (a2) having a weight average molecular weight of less than 6,000, wherein the cross-linking group is bonded directly or via a linking group to a site containing at least one siloxane bond,
The site containing at least one of the fluorine atom and the siloxane bond of the compound (a1) is a site containing a fluoroalkyl group and at least one siloxane bond represented by the following general formula (P),
The site containing at least one of the fluorine atom and the siloxane bond of the compound (a2) is a site containing a siloxane bond represented by the following general formula (P),
The compound (a2) is
A compound having one group represented by the following general formula (M-2),
A compound having one group represented by the following general formula (M-3),
A compound having two groups represented by the following general formula (M-1),
A compound having two groups represented by the following general formula (M-2), or
A compound having two groups represented by the following general formula (M-3),
An antireflection film having a region in which a content of the slip agent (a) is 51% or more in a material distribution in a cross-sectional direction of the region (S).

In formula (P), Rp ¹ and Rp ² each independently represent a hydrogen atom, a monovalent hydrocarbon group, an alkoxy group, or an aryloxy group. n represents an integer of 2 or more.

In Formula (M-1), R ₁ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkyloxy group, an alkenyloxy group, an alkyloxyalkyl group, or an alkenyloxyalkyl group. R ₁₁ and R ₁₂ each independently represent a hydrogen atom or a methyl group. * Represents a bonding position.
In Formula (M-2), R _{21 to} R ₂₃ each independently represent a hydrogen atom or a methyl group. * Represents a bonding position.
In Formula (M-3), R _{31 to} R ₃₅ each independently represent a hydrogen atom or a methyl group. * Represents a bonding position.
[2]
The reflectance of the antireflection film after rubbing the outermost surface of the antireflection layer opposite to the surface on the substrate side with steel wool 10 times under the condition of a load of 200 g is R _A , before rubbing with steel wool. when the reflectance of the antireflection film was R _0, the reflectivity changes represented by R _a -R ₀ is not more than 0.25%, the antireflection film as described in [1].
[3]
The antireflection film according to [1] or [2], wherein the crosslinking group of the slip agent (a) is a (meth) acryloyl group.
[4]
The site according to any one of [1] to [3], wherein the site containing at least one of the fluorine atom and the siloxane bond in the slip agent (a) is a polydimethylsiloxane group or a polyether-modified dimethylsiloxane group. Anti-reflection film.
[5]
[1] to [1], wherein the slipping agent (a) is the compound (a1), and the compound (a1) has the cross-linking group linked to the main chain by a CC bond or a CO bond; 4) The antireflection film according to any one of the above items.
[6]
The above-mentioned slipping agent (a) is the above-mentioned compound (a2), and the above-mentioned compound (a2) is such that a site containing at least one of the above-mentioned fluorine atom and siloxane bond and the above-mentioned crosslinking group are a C—C bond or a C—O bond. The antireflection film according to any one of [1] to [4], which is bonded via a bond.
[7]
The antireflection film according to any one of [1] to [6], wherein the antireflection layer has particles (d) having an average primary particle size of 250 nm or less.
[8]
The antireflection film according to [7], wherein the antireflection layer has an uneven shape formed by the particles (d) on a surface of the antireflection layer opposite to the substrate side.
[9]
The antireflection film according to any one of [1] to [8], wherein the substrate has a visible light transmittance of 80% or more.
[10]
The antireflection film according to [8], wherein the antireflection layer does not include a plurality of the particles (d) in a direction orthogonal to the surface of the base material.
[11]
A method for producing an antireflection film according to [8],
On the substrate,
A composition containing the above-mentioned slipping agent (a), the above-mentioned curable compound (b), the above-mentioned photopolymerization initiator (c), the above-mentioned particles (d), and a solvent is applied, and the above-mentioned particles (d (1) providing a layer (A) in which the thickness of the part where no) is present is at least 0.8 times the average primary particle size of the particles (d);
A step (2) of curing a part of the curable compound (b) in the layer (A) to obtain a cured compound (bc);
A part of a compound selected from the group consisting of the curable compound (b) and the compound (bc) in the layer (A) is caused to penetrate or volatilize the base material by heating, and the layer (A) (3) forming an uneven shape composed of the particles (d) on the outermost surface opposite to the substrate side;
A compound selected from the group consisting of the slip agent (a), the curable compound (b) and the compound (bc) remaining in the layer (A) is cured to form the antireflection layer. Step (4),
In this order, the method for producing an antireflection film.
[12]
Between step (1) and step (2), between step (2) and step (3), or between step (3) and step (4)
A step (E1) of providing a layer (E) containing a compound (e) incompatible with the curable compound (b) on the surface of the layer (A) opposite to the surface on the substrate side. Have
The method according to [11], further comprising a step (E2) of removing the layer (E) after the step (2), the step (3), or the step (4) performed subsequent to the step (E1). Manufacturing method of antireflection film.
The present invention is the invention according to the above [1] to [12], but other matters will be described below for reference.
<1>
On the substrate, having at least one antireflection layer,
The antireflection layer has a thickness (S) of 20 nm or less in a direction from the outermost surface on the opposite side to the surface on the substrate side toward the substrate,
A slip agent (a) having three or more cross-linking groups in one molecule, having a cross-linking group equivalent of 450 or less, and having a site containing at least one of a fluorine atom and a siloxane bond;
A curable compound (b) having at least three crosslinking groups in one molecule, having a crosslinking group equivalent of 450 or less, and having neither a fluorine atom nor a siloxane bond;
A photopolymerization initiator (c), and a cured product of a curable composition containing:
An antireflection film having a region in which a content of the slip agent (a) is 51% or more in a material distribution in a cross-sectional direction of the region (S).
<2>
The reflectance of the antireflection film after rubbing the outermost surface of the antireflection layer opposite to the substrate side with steel wool 10 times under the condition of a load of 200 g is R _A , before rubbing with steel wool. when the reflectance of the antireflection film was _{R 0,} the reflectivity changes represented by R a -R ₀ it is not more than 0.25%, the anti-reflection film according to <1>.
<3>
The antireflection film according to <1> or <2>, wherein the crosslinking group of the slip agent (a) is a (meth) acryloyl group.
<4>
The antireflection film according to any one of <1> to <3>, wherein the portion of the slip agent (a) containing at least one of the fluorine atom and the siloxane bond is a fluoroalkyl group.
<5>
The site according to any one of <1> to <3>, wherein the site containing at least one of the fluorine atom and the siloxane bond in the slip agent (a) is a polydimethylsiloxane group or a polyether-modified dimethylsiloxane group. Anti-reflection film.
<6>
The slipping agent (a) is a compound (a1) having a site containing at least one of the fluorine atom and the siloxane bond in a side chain and the crosslinking group, and having a weight average molecular weight of 6,000 or more, <4> Or the antireflection film according to <5>.
<7>
The anti-reflection film according to <6>, wherein the compound (a1) has the cross-linking group linked to the main chain by a CC bond or a CO bond.
<8>
The slipping agent (a) is a compound (a2) having a weight average molecular weight of less than 6,000, in which the crosslinking group is bonded directly or via a linking group to a site containing at least one of the fluorine atom and the siloxane bond. The antireflection film according to <4> or <5>.
<9>
The compound (a2) is
A compound having one group represented by the following general formula (M-2),
A compound having one group represented by the following general formula (M-3),
A compound having two groups represented by the following general formula (M-1),
A compound having two groups represented by the following general formula (M-2), or
The antireflection film according to <8>, which is a compound having two groups represented by the following general formula (M-3).

In Formula (M-1), R ₁ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkyloxy group, an alkenyloxy group, an alkyloxyalkyl group, or an alkenyloxyalkyl group. R ₁₁ and R ₁₂ each independently represent a hydrogen atom or a methyl group. * Represents a bonding position.
In Formula (M-2), R _{21 to} R ₂₃ each independently represent a hydrogen atom or a methyl group. * Represents a bonding position.
In Formula (M-3), R _{31 to} R ₃₅ each independently represent a hydrogen atom or a methyl group. * Represents a bonding position.
<10>
<8> The reflection according to <8>, wherein the compound (a2) has a site containing at least one of the fluorine atom and the siloxane bond, and the cross-linking group bonded via a CC bond or a CO bond. Prevention film.
<11>
The antireflection film according to any one of <1> to <10>, wherein the antireflection layer has particles (d) having an average primary particle size of 250 nm or less.
<12>
The antireflection film according to <11>, wherein the antireflection layer has an uneven shape formed by the particles (d) on a surface of the antireflection layer opposite to the substrate side.
<13>
The antireflection film according to any one of <1> to <12>, wherein the substrate has a visible light transmittance of 80% or more.
<14>
<12> The antireflection film according to <12>, wherein the antireflection layer does not include a plurality of the particles (d) in a direction orthogonal to the surface of the substrate.
<15>
A method for producing an antireflection film according to <12>,
On the substrate,
A composition containing the above-mentioned slipping agent (a), the above-mentioned curable compound (b), the above-mentioned photopolymerization initiator (c), the above-mentioned particles (d), and a solvent is applied, and the above-mentioned particles (d (1) providing a layer (A) in which the thickness of a portion where no) is present is at least 0.8 times the average primary particle size of the particles (d);
A step (2) of curing a part of the curable compound (b) in the layer (A) to obtain a cured compound (bc);
Part of the compound selected from the group consisting of the curable compound (b) and the compound (bc) in the layer (A) is made to penetrate or volatilize the substrate by heating, and the layer (A) A) forming an uneven shape composed of the particles (d) on the outermost surface opposite to the substrate side;
A compound selected from the group consisting of the slip agent (a), the curable compound (b) and the compound (bc) remaining in the layer (A) is cured to form the antireflection layer. Step (4),
In this order, the method for producing an antireflection film.
<16>
Between step (1) and step (2), between step (2) and step (3), or between step (3) and step (4)
A step (E1) of providing a layer (E) containing a compound (e) incompatible with the curable compound (b) on the surface of the layer (A) opposite to the surface on the substrate side. Have
<15> The method according to <15>, further comprising a step (E2) of removing the layer (E) after the step (2), the step (3), or the step (4) performed subsequent to the step (E1). Manufacturing method of antireflection film.

  According to the present invention, it is possible to provide a practical anti-reflection film having excellent anti-reflection performance, a small change in reflectance before and after a scratch resistance test, and excellent practical scratch resistance. It is possible to propose a method capable of easily producing a film.

It is a schematic diagram which shows an example of the manufacturing method of the antireflection film of this invention. It is a cross section showing an example of an antireflection film of the present invention. It is a cross section showing an example of an antireflection film of the present invention. It is a cross section showing an example of an antireflection film of the present invention.

Hereinafter, preferred embodiments according to the present invention will be described in detail. The description of the components described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
Further, “(meth) acrylate” represents at least one of acrylate and methacrylate, “(meth) acryl” represents at least one of acryl and methacryl, and “(meth) acryloyl” represents at least one of acryloyl and methacryloyl. .

[Anti-reflective film]
The antireflection film of the present invention,
On the substrate, having at least one antireflection layer,
The antireflection layer has a thickness (S) of 20 nm or less in a direction from the outermost surface on the opposite side to the surface on the substrate side toward the substrate,
A slip agent (a) having three or more cross-linking groups in one molecule, having a cross-linking group equivalent of 450 or less, and having a site containing at least one of a fluorine atom and a siloxane bond;
A curable compound (b) having at least three crosslinking groups in one molecule, having a crosslinking group equivalent of 450 or less, and having neither a fluorine atom nor a siloxane bond;
A photopolymerization initiator (c), and a cured product of a curable composition containing:
An antireflection film having a region where the content of the slip agent (a) is 51% or more in the material distribution in the cross-sectional direction of the region (S).
3 and 4 are schematic cross-sectional views each showing an example of the antireflection film of the present invention.

<Slip agent (a)>
The slip agent (a) will be described.
The slipping agent (a) has three or more crosslinking groups in one molecule, a crosslinking group equivalent of 450 or less, and a site containing at least one of a fluorine atom and a siloxane bond (hereinafter, this site is referred to as a “low friction site”). Also called).
Examples of the crosslinking group include a radical reactive group or a reactive group other than the radical reactive group, and a radical reactive group is preferable.
Examples of the radical reactive group include groups having an unsaturated bond capable of addition polymerization (for example, (meth) acryloyl group, (meth) acrylamide group, (meth) acrylonitrile group, allyl group, vinyl group, styrene structure, vinyl ether structure, acetylene Structures, etc.), -SH, -PH, SiH, -GeH, disulfide structures and the like, and a polymerizable functional group such as a (meth) acryloyl group, a vinyl group, a styryl group, an allyl group (a polymerizable carbon-carbon group). (A group having a saturated double bond) is preferable. Among them, a (meth) acryloyl group and —C (O) OCH ＝ CH ₂ are preferable, and a (meth) acryloyl group is most preferable.
Examples of the reactive group other than the radical reactive group include an epoxy group, an amino group, a boronic acid group, a boronic ester group, an oxiranyl group, an oxetanyl group, a hydroxyl group, a carboxyl group, and an isocyanate group.

The crosslinking group equivalent of the slipping agent (a) is a value obtained by dividing the molecular weight of the slipping agent (a) by the number of crosslinking groups contained in the slipping agent (a), and is 450 or less from the viewpoint of the film strength after curing. And more preferably 350 or less, and even more preferably 300 or less.
In addition, for example, when the crosslinking group is an acryloyl group or a methacryloyl group, the crosslinking group equivalent may be referred to as an acrylic equivalent.

From the viewpoint of uneven distribution in the antireflection layer, the slipping agent (a) is a compound (a1) having a low friction site and a crosslinking group in a side chain and having a weight average molecular weight of 6,000 or more, or From the viewpoint of the strength of the outermost surface, it is preferable that the compound (a2) having a weight average molecular weight of less than 6,000, in which a crosslinking group is directly or via a linking group bonded to a low friction site.
The compound (a1) is preferably a polymer, and the compound (a1) preferably has a weight average molecular weight of 6,000 to 100,000, and more preferably 8,000 to 80,000.
The compound (a2) is preferably a monomer or an oligomer, and the compound (a2) preferably has a weight average molecular weight of 900 to 6,000, and more preferably 1300 to 5000.
The weight average molecular weight of the slipping agent (a) is determined by the same method as the weight average molecular weight of the curable compound (b) described later.

From the viewpoint of chemical resistance and durability, the compound (a1) preferably has a crosslinking group linked to the main chain by a CC bond or a CO bond.
Similarly, from the viewpoint of chemical resistance and durability, the compound (a2) preferably has a low friction site and a cross-linking group bonded via a CC bond or a CO bond.

The compound (a1) preferably has a repeating unit having a low friction site in a side chain and a repeating unit having a crosslinking group in a side chain.
As the repeating unit having a crosslinking group in the side chain, those described in JP-A-2009-79126, [0028] to [0044], can be referred to.

The compound (a2) is
A compound having one group represented by the following general formula (M-2),
A compound having one group represented by the following general formula (M-3),
A compound having two groups represented by the following general formula (M-1),
A compound having two groups represented by the following general formula (M-2), or
It is preferably a compound having two groups represented by the following general formula (M-3).

In Formula (M-1), R ₁ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkyloxy group, an alkenyloxy group, an alkyloxyalkyl group, or an alkenyloxyalkyl group. R ₁₁ and R ₁₂ each independently represent a hydrogen atom or a methyl group. * Represents a bonding position.
In Formula (M-2), R _{21 to} R ₂₃ each independently represent a hydrogen atom or a methyl group. * Represents a bonding position.
In Formula (M-3), R _{31 to} R ₃₅ each independently represent a hydrogen atom or a methyl group. * Represents a bonding position.

When the compound (a2) is a compound having one group represented by the general formula (M-2), the compound having a cross-linking group at one end of a main chain including a low friction site. It is preferable that the group represented by formula (M-2) is bonded directly or via a linking group.
When the compound (a2) is a compound having one group represented by the general formula (M-3), the compound is a group having a cross-linking group at one end of a main chain including a low friction site. It is preferable that the group represented by formula (M-3) is bonded directly or via a linking group.
When the compound (a2) is a compound having two groups represented by the general formula (M-1), the compound having a cross-linking group at both ends of a main chain including a low friction site. It is preferable that the group represented by formula (M-1) is bonded directly or via a linking group. Here, the two groups represented by the general formula (M-1) may be the same or different.
When the compound (a2) is a compound having two groups represented by the general formula (M-2), the compound having a cross-linking group at both ends of a main chain containing a low friction site. It is preferable that the group represented by formula (M-2) is bonded directly or via a linking group. Here, two groups represented by the general formula (M-2) may be the same or different.
When the compound (a2) is a compound having two groups represented by the general formula (M-3), the compound having a cross-linking group at both ends of a main chain including a low friction site. It is preferable that the group represented by formula (M-3) is bonded directly or via a linking group. Here, two groups represented by the general formula (M-3) may be the same or different.

  When the slipping agent (a) has a low friction site containing a fluorine atom, the site containing a fluorine atom is preferably a fluoroalkyl group. The slip agent (a) having a portion containing a fluorine atom can be represented by, for example, a structure represented by the following general formula (1), but the present invention is not limited thereto. In the present invention, the hydrocarbon chain may be represented by a simplified structural formula in which the symbols of carbon (C) and hydrogen (H) are omitted in the chemical formula.

  General formula (1)

  In the general formula (1), R represents a hydrogen atom or a fluorine atom.

  The general formula (P) shows the structure of the siloxane bond when the slip agent (a) has a low friction site containing a siloxane bond.

In the general formula (P), Rp ¹ and Rp ² each independently represent a hydrogen atom, a monovalent hydrocarbon group, an alkoxy group, or an aryloxy group. n represents an integer of 2 or more.
Examples of the monovalent hydrocarbon group include an alkyl group, an aryl group, an alkenyl group, an alkynyl group, and an aralkyl group.
Rp ¹ and Rp ² are a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms. It is preferably, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, more preferably an alkyl group having 1 to 20 carbon atoms, Most preferably, it is a methyl group.
Further, n is preferably an integer of 6 to 100, more preferably n is an integer of 8 to 65, and most preferably n is an integer of 10 to 35.

A polydimethylsiloxane group or a polyether-modified dimethylsiloxane group is useful as a site containing a siloxane bond of the slipping agent (a). In the present invention, in particular, a polydimethylsiloxane group having a repeating number n of 6 to 100 or a polyether-modified dimethylsiloxane group is more preferable, n is more preferably 8 to 65, and n is most preferably 10 to 35.
When the number of repetitions n of the polydimethylsiloxane group or the polyether-modified dimethylsiloxane group is 6 or more, hydrophobicity is exhibited, the uneven distribution ability at the air interface is increased, and a low friction site can be exposed on the surface, And it is not too short even as a low friction part, and can improve slipperiness. When the number of repetitions n is 100 or less, uneven distribution is sufficient, the density of cross-linking groups does not decrease, the strength of the film obtained by cross-linking increases, and the film effectively functions in a scratch resistance test.

  As the slipping agent (a) having a site containing a siloxane bond, a silicone-based polymer (compound (A1)) and a silicone-based monomer or oligomer (compound (A2)) can be used. The compound (A1) and the compound (A2) will be described in detail below.

{Compound (A1)}
The compound (A1) is a case where the low friction site is a site having a siloxane bond in the compound (a1). That is, the compound (A1) is a compound (silicone polymer) having a site containing a siloxane bond in a side chain and a crosslinking group, and having a weight average molecular weight of 6,000 or more. Specific examples of the compound (A1) are shown in the following general formula (2).

  General formula (2)

In the general formula (2), R ¹ represents a hydrogen atom or a methyl group, R ² represents a divalent connecting chain, R ³ represents a hydrogen atom or a monovalent organic group, and n is an integer of 5 to 100. Represents R ¹ , R ² , and R ³ in each repeating unit may be the same or different.

In the general formula (2), R ² represents a divalent linking chain, specifically, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, or a linking group (for example, an ether bond, an ester) A substituted or unsubstituted alkylene group having a bond or an amide bond), a substituted or unsubstituted arylene group having a connecting group therein, and a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, An alkylene group having a linking group is preferable, an unsubstituted alkylene group, an unsubstituted arylene group, an alkylene group having an ether bond or an ester bond therein is more preferable, and an unsubstituted alkylene group, an ether bond or an ester bond therein. An alkylene group having the formula is particularly preferred. Examples of the substituent include a halogen, a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an alkyl group, and an aryl group. These substituents may be further substituted.
N in the general formula (2) represents an integer of 5 to 100, preferably an integer of 7 to 65, and more preferably an integer of 9 to 35.

  Among the silicon-containing polymers (A) described in paragraphs [0012] to [0048] of JP-A-2009-79126, P-10 and P-12 to P-14 whose acrylic equivalents satisfy the range of the present invention are slip. It can be appropriately used as the agent (a). Specific examples of the slip agent (a) having a siloxane bond are shown below, but the present invention is not limited thereto. In the following specific examples, the numbers attached to the parentheses of each monomer unit represent the molar ratio of each monomer unit in the polymer.

  Examples of commercially available silicone-based polymers having the structure represented by the general formula (2) include Acryt 8SS-723 (manufactured by Taisei Fine Chemical Co., Ltd.) and Acryt 8SS-1024 (manufactured by Taisei Fine Chemical Co., Ltd.).

{Compound (A2)}
The compound (A2) is the case where the low friction site is a site having a siloxane bond in the compound (a2). That is, the compound (A2) is a compound having a weight average molecular weight of less than 6,000 (silicone monomer or oligomer) in which a crosslinking group is directly or via a linking group at a site having a siloxane bond.

Examples of the silicone-based monomer or oligomer having a crosslinking group that can be suitably used as the compound (A2) include a compound represented by the following general formula (4) and a compound represented by the following general formula (5). However, the present invention is not limited to these.
The compound represented by the following general formula (4) has a group represented by the above general formula (M-3), which is a group having a cross-linking group at one end of a main chain containing a low friction site, and a linking group. Is a compound bonded through
The compound represented by the following general formula (5) is obtained by linking a group represented by the above general formula (M-2), which is a group having a crosslinking group, to one end of a main chain containing a low friction site. Is a compound bonded through

  General formula (4)

In the general formula (4), R ⁴¹ represents a divalent linking chain, R ⁴² represents a hydrogen atom or a monovalent organic group, and n represents an integer of 4 to 100.

In the general formula (4), R ⁴¹ represents a divalent linking chain, specifically, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, or a linking group (for example, ether bond, ester A substituted or unsubstituted alkylene group having a bond or an amide bond), a substituted or unsubstituted arylene group having a connecting group therein, and a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, An alkylene group having a linking group is preferable, an unsubstituted alkylene group, an unsubstituted arylene group, and an alkylene group having an ether bond or an ester bond therein are more preferable. An alkylene group having the formula is particularly preferred. Examples of the substituent include a halogen, a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an alkyl group, and an aryl group. These substituents may be further substituted.
R ⁴¹ in the general formula (4) is preferably an unsubstituted alkylene group having an ether bond or the like inside, and more preferably * (CH ₂ ) ₃ *.
R ⁴² in the general formula (4) represents a hydrogen atom or a monovalent organic group, and is preferably a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms.
N in the general formula (4) represents an integer of 4 to 100, preferably an integer of 6 to 65, and more preferably an integer of 8 to 35.

Specific examples of the compound represented by the general formula (4) include the following compounds (S-1) and (S-2). However, the present invention is not limited to these.
Compound (S-1): a compound of the above general formula (4), wherein n is 10, R ⁴¹ is — (CH ₂ ) ₃ —, and R ⁴² is CH ₃ .
Compound (S-2): a compound of the above formula (4), wherein n is 21, R ⁴¹ is — (CH ₂ ) ₃ —, and R ⁴² is CH ₃ .

  General formula (5)

In Formula (5), R ⁵¹ represents a divalent linking chain, R ⁵² represents a hydrogen atom or a monovalent organic group, and n represents an integer of 2 to 100.

In formula (5), specific examples and preferred ranges of R ⁵¹ and R ⁵² are the same as those of R ⁴¹ and R ⁴² in formula (4), respectively.
The preferred range of n in the general formula (5) is the same as n in the general formula (4).
Specific examples of the compound represented by the general formula (5) include the following compound (S-3). However, the present invention is not limited to these.
Compound (S-3): a compound in which n is 10, R ⁵¹ is — (CH ₂ ) ₃ —, and R ⁵² is CH ₃ in the general formula (5).

In addition, in the aforementioned general formula (4), the following compound (S-9), which is a compound in which n is 10, R ⁴¹ is —CONH (CH ₂ ) ₃ —, and R ⁴² is —CH ₃ , is also provided. preferable.
(S-9)

In the above general formula (5), the following compound (S-10), which is a compound in which n is 10, R ⁵¹ is —CONH (CH ₂ ) ₃ —, and R ⁵² is —CH ₃ , is also preferable.

  (S-10)

Examples of the silicone-based monomer or oligomer having a crosslinking group that can be suitably used as the compound (A2) include a compound represented by the general formula (4) and a compound represented by the general formula (5). Examples further include a compound represented by the following general formula (6) and a compound represented by the following general formula (7), but the present invention is not limited thereto.
The compound represented by the following general formula (6) has a group represented by the above general formula (M-3) which is a group having a cross-linking group at both ends of a main chain containing a low friction site. Is a compound bonded through
The compound represented by the following general formula (6) has a group represented by the above general formula (M-2) which is a group having a cross-linking group at one end of a main chain containing a low friction site. And a group having a cross-linking group represented by the general formula (M-2), which is a group having a cross-linking group, is bonded to the other end of the main chain including the low friction site via a linking group. Compound.

  General formula (6)

In Formula (6), R ⁶¹ and R ⁶² each independently represent a divalent linking chain, and n represents an integer of 4 to 100.
Specific examples and preferred ranges of R ⁶¹ and R ^{62 in} the general formula (6) are the same as those of R ⁴¹ in the general formula (4).
The preferred range of n in the general formula (6) is the same as n in the general formula (4).

Specific examples of the compound represented by the general formula (6) include the following compounds (S-4) to (S-6). However, the present invention is not limited to these.
Compound (S-4): a compound in the above formula (6), wherein n is 9, and R ⁶¹ and R ⁶² are — (CH ₂ ) ₃ —.
Compound (S-5): a compound in the above formula (6), wherein n is 20, and R ⁶¹ and R ⁶² are — (CH ₂ ) ₃ —.
Compound (S-6): a compound of the above general formula (6), wherein n is 40 and R ⁶¹ and R ⁶² are — (CH ₂ ) ₃ —.

  General formula (7)

In Formula (7), R ⁷¹ and R ⁷² each independently represent a divalent linking chain, and n represents an integer of 2 to 100.
Specific examples and preferred ranges of R ⁷¹ and R ^{72 in} the general formula (7) are the same as those of R ⁴¹ in the general formula (4).
The preferred range of n in the general formula (7) is the same as n in the general formula (4).
Specific examples of the compound represented by the general formula (7) include the following compounds (S-7) and (S-8). However, the present invention is not limited to these.
Compound (S-7): a compound of the above formula (7), wherein n is 20, and R ⁷¹ and R ⁷² are — (CH ₂ ) ₃ —.
Compound (S-8): a compound in the above formula (7), wherein n is 40 and R ⁷¹ and R ⁷² are — (CH ₂ ) ₃ —.

In addition, in the aforementioned general formula (6), the following compound (S-11), which is a compound in which n is 10 and R ⁶¹ and R ⁶² are —CONH (CH ₂ ) ₃ —, is also preferable.
(S-11)

In the aforementioned general formula (7), the following compound (S-12), which is a compound in which n is 10 and R ⁷¹ and R ⁷² are —CONH (CH ₂ ) ₃ —, is also preferable.

  (S-12)

<Curable compound (b)>
The curable compound (b) is a compound having at least three crosslinking groups in one molecule, having a crosslinking group equivalent of 450 or less, and having neither a fluorine atom nor a siloxane bond.
Specific examples and preferred ranges of the crosslinking group of the curable compound (b) are the same as those of the above-mentioned crosslinking agent (a).
The crosslinking group equivalent of the curable compound (b) is a value obtained by dividing the molecular weight of the curable compound (b) by the number of crosslinking groups contained in the curable compound (b), and is 450 or less from the viewpoint of film strength. And more preferably 350 or less, and even more preferably 250 or less.
It is preferable to use at least one compound having a radical reactive group as the curable compound (b).
Examples of the radical reactive group include groups having an unsaturated bond capable of addition polymerization (for example, (meth) acryloyl group, (meth) acrylamide group, (meth) acrylonitrile group, allyl group, vinyl group, styrene structure, vinyl ether structure, acetylene Structure, etc.), -SH, -PH, SiH, -GeH, disulfide structure and the like.
As the curable compound (b), at least one compound having a polymerizable functional group (polymerizable carbon-carbon unsaturated double bond) such as a (meth) acryloyl group, a vinyl group, a styryl group, an allyl group is used. It is preferable to use at least one compound having a (meth) acryloyl group and —C (O) OCH ＝ CH _2, and it is more preferable to use at least one compound having a (meth) acryloyl group. It is further preferable to use at least one compound having two or more (meth) acryloyl groups in one molecule.
As the curable compound (b), one compound may be used alone, or two or more compounds may be used in combination.
In particular, when the antireflection film of the present invention uses a substrate with a hard coat layer as the substrate, at least two types of curable compounds are used as the curable compound (b), at least one of which is radically reactive. A compound having a group, and at least one other is a compound that penetrates the substrate in step (3) of the method for producing an antireflection film, does not have a radical reactive group, and is other than a radical reactive group. It is preferable that the compound has a reactive group of

Examples of the curable compound (b) include the following curable compounds (b-1) to (b-3). Of these, it is preferable to use two or more thereof, and it is more preferable to use all three together. preferable.
Curable compound (b-1): a compound having a molecular weight of 400 or more and having a radical reactive group Curable compound (b-2): a silane coupling agent having a radical reactive group Curable compound (b-3) : A compound having a molecular weight of less than 400, having no radical reactive group and having a reactive group other than the radical reactive group, or a compound having a molecular weight of less than 300 and volatilizing upon heating

  When the molecular weight of the curable compound (b) is uniquely determined from the structural formula of the curable compound, the molecular weight is determined from the structural formula, and is uniquely determined from the structural formula such as having a distribution like a polymer compound. If not determined, the weight average molecular weight measured using gel permeation chromatography is used.

The weight average molecular weight in the present invention is a value measured by gel permeation chromatography (GPC) under the following conditions.
[Solvent] Tetrahydrofuran [Device name] TOSOH HLC-8220GPC
[Column] TOSOH TSKgel Super HZM-H
(4.6mm x 15cm) connected and used.
[Column temperature] 25 ° C
[Sample concentration] 0.1% by mass
[Flow rate] 0.35 ml / min
[Calibration Curve] TSKOH standard polystyrene manufactured by TOSOH A calibration curve using 7 samples from weight average molecular weight (Mw) = 2800000 to 1050 was used.

<< Curable compound (b-1) >>
The curable compound (b-1) is a compound having a molecular weight of 400 or more and having a radical reactive group.
The curable compound (b-1) is preferably a compound that hardly penetrates the substrate.
The molecular weight of the curable compound (b-1) is preferably from 400 to 100,000, more preferably from 1,000 to 50,000.
The curable compound (b-1) preferably has a functional group equivalent represented by (molecular weight / radical reactive group amount) of 450 or less, more preferably 400 or less, and preferably 350 or less. Is more preferred.
It is preferable that the curable compound (b-1) does not have a hydrolyzable silane coupling group represented by an alkoxysilyl group (that is, it is not a silane coupling agent).

Examples of the curable compound (b-1) include (meth) acrylic diesters of alkylene glycol, (meth) acrylic diester of polyoxyalkylene glycol, (meth) acrylic diester of polyhydric alcohol, ethylene oxide and propylene. Examples of the oxide adduct include (meth) acrylic acid diesters, epoxy (meth) acrylates, urethane (meth) acrylates, and polyester (meth) acrylates.
Specific examples of the curable compound (b-1) include KAYARAD DPHA, DPHA-2C, PET-30, TMPTA, TPA-320, TPA-330, RP-1040, T-1420, D-310, DPCA-20, DPCA-30, DPCA-60, GPO-303 (manufactured by Nippon Kayaku Co., Ltd.), NK ester A-TMPT, A-TMMT, A-TMM3, A- TMM3L, A-9550 (manufactured by Shin-Nakamura Chemical Co., Ltd.), V # 3PA, V # 400, V # 36095D, V # 1000, V # 1080, Biscoat # 802 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), etc. Of poly (acrylic acid) and (meth) acrylic acid, dendrimer type polyfunctional acryle such as Sirius-501, SUBARU-501 (manufactured by Osaka Organic Chemical Industry Co., Ltd.) Can be mentioned. Also, UV-1400B, UV-1700B, UV-6300B, UV-7550B, UV-7600B, UV-7605B, UV-7610B, UV-7620EA, UV-7630B, UV-7640B UV-6630B, UV-7000B, UV-7510B, UV-7461TE, UV-3000B, UV-3200B, UV-3210EA, UV-3310EA, UV-3310B, UV-3500BA UV-3520TL, UV-3700B, UV-6100B, UV-6640B, UV-2000B, UV-2010B, UV-2250EA, UV-2750B (manufactured by Nippon Synthetic Chemical Co., Ltd.), UL-503LN (manufactured by Kyoeisha Chemical Co., Ltd.), Unidick 17-80 17-813, V-4030, V-4000BA (manufactured by Dainippon Ink and Chemicals, Inc.), EB-1290K, EB-220, EB-5129, EB-1830, EB-4858 (Daicel UCB ( AU-2010, AU-2020 (manufactured by Tokushiki Co., Ltd.), Aronix M-1960 (manufactured by Toagosei Co., Ltd.), Art Resin UN-3320HA, UN-3320HC, UN-3320HS, UN -904 (manufactured by Negami Industry Co., Ltd.), NK Oligo U-4HA, U-15HA (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), etc., trifunctional or higher functional urethane acrylate compound, ARONIX M-8100, M-8030, M -9050 (manufactured by Toagosei Co., Ltd., KRM-8307 (manufactured by Daicel Cytec Co., Ltd.)) Things like can also be suitably used.

<< Curable compound (b-2) >>
The curable compound (b-2) is a silane coupling agent having a radical reactive group.
The molecular weight of the curable compound (b-2) is preferably from 100 to 5,000, more preferably from 200 to 2,000.
The curable compound (b-2) is preferably a compound that hardly penetrates the substrate.
The curable compound (b-2) has a functional group equivalent represented by (molecular weight / radical reactive group amount) of preferably 450 or less, more preferably 400 or less, and more preferably 350 or less. Is more preferred.
Specific examples of the curable compound (b-2) include 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropyldimethylmethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 2- (meth) acryloxyethyltrimethoxysilane, 2- (meth) acryloxyethyltriethoxysilane, 4 -(Meth) acryloxybutyltrimethoxysilane, 4- (meth) acryloxybutyltriethoxysilane, and the like. Specifically, KBM-503 and KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.) and silane coupling agents X-12-1048, X-12-1049, and X-12 described in JP-A-2014-123091. 1050 (manufactured by Shin-Etsu Chemical Co., Ltd.) or the like can be used.
Further, an acryloyl group-containing trimethoxysilane represented by the following formula (10) can also be preferably used.
Equation (10)

{Curable compound (b-3)}
The curable compound (b-3) has a molecular weight of less than 400, does not have a radical reactive group, and has a reactive group other than the radical reactive group.
The curable compound (b-3) is preferably a compound that hardly penetrates the substrate at 25 ° C. and easily penetrates the substrate when heated.
The reactive group other than the radical reactive group contained in the curable compound (b-3) includes a group that reacts with a compound constituting a base material (or a functional layer when the base material has a functional layer such as a hard coat layer). And an epoxy group, an amino group, a boronic acid group, a boronic ester group, an oxiranyl group, an oxetanyl group, a hydroxyl group, a carboxyl group, and an isocyanate group.
The molecular weight of the curable compound (b-3) is preferably from 100 to less than 400, more preferably from 200 to 300.
The curable compound (b-3) preferably has two or more reactive groups other than the radical reactive group.
Specific examples of the curable compound (b-3) include Celloxide 2021P, Celloxide 2081, Epolide GT-301, Epolide GT-401, EHPE3150CE (all manufactured by Daicel Chemical Industries, Ltd.), OXT-121, and OXT-221. OX-SQ, PNOX-1009 (manufactured by Toagosei Co., Ltd.), KBM-303, KBM-402, KBM-403, KBE-402, KBE-403, KBM-4803 (manufactured by Shin-Etsu Chemical Co., Ltd.) )).

  The content of the curable compound (b) with respect to the total solid content in the curable composition is preferably from 50 to 98% by mass, more preferably from 55 to 95% by mass, and still more preferably from 60 to 90% by mass.

<Photopolymerization initiator (c)>
The region (S) of the antireflection layer in the present invention contains a cured product of the curable composition containing the above-mentioned slipping agent (a), the above-mentioned curable compound (b) and the photopolymerization initiator (c).
Examples of the photopolymerization initiator (c) include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfides Compounds, fluoroamine compounds, aromatic sulfoniums, lophine dimers, onium salts, borate salts, active esters, active halogens, inorganic complexes, coumarins and the like. Specific examples, preferred embodiments, commercially available products, and the like of the photopolymerization initiator (c) are described in Paragraphs [0133] to [0151] of JP-A-2009-098658. Can be used.

  "Latest UV Curing Technology" {Technical Information Association Ltd.} (1991), p. 159 and "Ultraviolet curing system" by Kiyomi Kato (1989, published by the General Technology Center), p. 65-148 also describe various examples, and are useful in the present invention as a photopolymerization initiator (c).

  The content of the photopolymerization initiator (c) is large enough to polymerize the polymerizable compound contained in the curable composition (composition for forming an antireflection layer), and small enough not to increase the starting point too much. From the viewpoint of setting the amount, it is preferably 0.5 to 8% by mass, more preferably 1 to 5% by mass, based on the total solids in the composition for forming an antireflection layer.

  In the region (S) of the antireflection layer in the present invention, a cured product of the curable composition containing the above-mentioned slipping agent (a), the above-mentioned curable compound (b) and the above-mentioned photopolymerization initiator (c) is used. However, the curable composition may contain other components.

The antireflection film of the present invention has a region where the content of the slip agent (a) is 51% or more in the material distribution in the cross-sectional direction of the region (S).
The content of the slipping agent (a) is determined based on the fluorine atom and silicone (siloxane bond) present in an arbitrary region (S) between the outermost surface of the antireflection layer and the surface on the side opposite to the substrate up to 20 nm. Is defined as X, and the total amount of fluorine atoms and silicone (siloxane bonds) in the film when the slip agent (a) is cured alone to form a film is represented by Y, 100 * (X / Y ) (Unit:%). Here, the material distribution in the cross-sectional direction of the anti-reflection layer included the slip agent (a) when the film was cut with a microtome and the cross-section was analyzed with a time-of-flight secondary ion mass spectrometer (TOF-SIMS). It is detected as a material distribution, and the film thickness in this region can also be measured from TOF-SIMS cross-sectional information.
The antireflection film of the present invention preferably has a region in which the content of the above-mentioned slipping agent (a) is 51% or more in the region (S), and preferably has a region of more than 55% and less than 100%. % Or more, and more preferably 70% or more.
When the region (S) has a region in which the content of the slip agent (a) is 51% or more, the slip agent (a) is not distributed to the inside of the antireflection layer (that is, the slip agent (a) (It is unevenly distributed near the outermost surface), and it is possible to improve the slipperiness and the film hardness.
Incidentally, the total amount of fluorine atoms and silicone (siloxane bond), F was measured by time-of-flight secondary ion mass spectrometry (TOF-SIMS) ^- measured by the ratio of the fragment or _Si 2 _C 5 _H 15 ^{O +} fragment or, It can be measured by the F / C or Si / C ratio measured by XPS (X-ray Photoelectron Spectroscopy) analysis in which the incident angle is appropriately adjusted. By measuring the single film obtained by curing only the slip agent (a) by TOF-SIMS or XPS, the content can be defined as 100%. By measuring the antireflection film of the present invention by the same measuring method as the single film. And the content in the antireflection film.

  The thickness of the antireflection layer of the antireflection film of the invention is preferably from 50 to 200 nm, more preferably from 60 to 190 nm.

(Base material)
The substrate is not particularly limited as long as it is a light-transmitting substrate generally used as a substrate of an antireflection film, but a plastic substrate or a glass substrate is preferable.
As the plastic substrate, various types can be used. For example, cellulose resins; cellulose acylates (triacetate cellulose, diacetyl cellulose, acetate butyrate cellulose) and the like; polyester resins; polyethylene terephthalate and the like, (meth) acrylic resins, polyurethane And a substrate containing cellulose acylate, polyethylene terephthalate, or (meth) acrylic resin, and preferably a substrate containing cellulose acylate. Is more preferable, and a cellulose acylate film is particularly preferable. As the cellulose acylate, a substrate or the like described in JP-A-2012-093723 can be preferably used.
The thickness of the substrate is usually about 10 μm to 1000 μm, but is preferably 20 μm to 200 μm, more preferably 25 μm to 100 μm from the viewpoint that handleability is good, high translucency is obtained, and sufficient strength is obtained. preferable.
As the translucency of the substrate, the transmittance of visible light (preferably, the average transmittance at a wavelength of 400 nm or more and 750 nm or less) is preferably 80% or more, and more preferably 90% or more.

The anti-reflection film of the present invention, the outermost surface of the anti-reflection layer opposite to the surface on the substrate side, the reflectance of the anti-reflection film after rubbing 10 times with steel wool under the condition of a load of 200 g, R _A , when the reflectance of the antireflection film before rubbing with steel wool and the _{R 0,} it is preferable that change in reflectance represented by R a -R ₀ it is not more than 0.25%, is 0.20% or less And more preferably 0.15% or less.
However, the reflectivity _RA was determined when the film surface was rubbed 10 times with steel wool, assuming that the rubbing speed was 13 cm / sec, the load was 200 g / cm ² , and the contact area between the steel wool and the antireflection film surface was 1 cm × 1 cm. Shows the reflectance.

<Particle (d)>
The antireflection layer of the antireflection film of the present invention preferably has particles (d) having an average primary particle size of 250 nm or less.
Examples of the particles (d) include metal oxide particles, resin particles, and organic-inorganic hybrid particles having a core of the metal oxide particles and a shell of the resin. Metal oxide particles are preferable from the viewpoint of excellent film strength.
Examples of the metal oxide particles include silica particles, titania particles, zirconia particles, antimony pentoxide particles, and the like. From the viewpoint, silica particles are preferred.
Examples of the resin particles include polymethyl methacrylate particles, polystyrene particles, and melamine particles.

The average primary particle diameter of the particles (d) is more preferably 150 nm or more and 250 nm or less, and even more preferably 170 nm or more and 220 nm or less, from the viewpoint that the particles can form a moth-eye structure.
As the particle (d), only one type may be used, or two or more types of particles having different average primary particle sizes may be used.

The average primary particle diameter of the particles (d) indicates a 50% particle diameter of the cumulative volume average particle diameter.
More specifically, particles are added to ethanol so as to have a content of 35% by mass, and dispersed by ultrasonic waves for 10 minutes or more to prepare a dispersion of particles. The dispersion is measured by an electron micrograph. You can do it. Dropping the dispersion liquid, taking a SEM (Scanning Electron Microscope) image, measuring the diameter of each of the 100 primary particles, calculating the volume thereof, and making the cumulative 50% particle diameter the average primary particle diameter. Can be. If the particles do not have a spherical diameter, the average of the major and minor diameters is regarded as the diameter of the primary particles.

  The shape of the particles (d) is most preferably spherical, but there is no problem even if the shape is other than spherical such as amorphous. The particles may be either crystalline or amorphous.

As the particles (d), it is preferable to use inorganic fine particles that have been subjected to a surface treatment in order to improve dispersibility in a coating solution, improve film strength, and prevent aggregation. Specific examples and preferable examples of the surface treatment method are the same as those described in [0119] to [0147] of JP-A-2007-298974.
In particular, from the viewpoint of imparting a binding property to a resin and improving the film strength, the particle surface is surface-modified with a compound having an unsaturated double bond and a functional group reactive with the particle surface, and the particle surface is not modified. It is preferable to provide a saturated double bond.

  Specific examples of particles having an average primary particle diameter of 150 nm or more and 250 nm or less include Seahoster KE-P20 (average primary particle diameter of 200 nm, amorphous silica manufactured by Nippon Shokubai Co., Ltd.), Eposter S (average primary particle diameter of 200 nm, Japan Melamine-formaldehyde condensate manufactured by Catalyst Co., Ltd., Eposter MA-MX100W (average primary particle diameter: 175 nm, cross-linked polymethyl methacrylate (PMMA) manufactured by Nippon Shokubai Co., Ltd.) can be preferably used.

The particles (d) are particularly preferably calcined silica particles because they have moderately large hydroxyl groups on the surface and are hard particles.
The calcined silica particles are produced by a known technique of calcining the silica particles after obtaining the silica particles by hydrolyzing and condensing a hydrolyzable silicon compound in an organic solvent containing water and a catalyst. For example, JP-A-2003-176121 and JP-A-2008-137854 can be referred to.
The silicon compound as a raw material for producing the calcined silica particles is not particularly limited, but chlorosilanes such as tetrachlorosilane, methyltrichlorosilane, phenyltrichlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, methylvinyldichlorosilane, trimethylchlorosilane, and methyldiphenylchlorosilane Compounds: tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, trimethoxyvinylsilane, triethoxyvinylsilane, 3-glycidoxypropyltrimethoxysilane, 3-chloro Propyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxy Silane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-chloropropylmethyldimethoxysilane, Alkoxysilane compounds such as diphenyldimethoxysilane, diphenyldiethoxysilane, dimethoxydiethoxysilane, trimethylmethoxysilane, trimethylethoxysilane; tetraacetoxysilane, methyltriacetoxysilane, phenyltriacetoxysilane, dimethyldiacetoxysilane, diphenyldiacetoxysilane Acyloxysilane compounds such as trimethylacetoxysilane and dimethylsilanediol, diphenylsilanediol, Silanol compounds such as chill silanol; and the like. Among the silane compounds exemplified above, the alkoxysilane compound is particularly preferable because it is more easily available and the obtained calcined silica particles do not contain a halogen atom as an impurity. As a preferred form of the calcined silica particles according to the present invention, it is preferable that the content of halogen atoms is substantially 0% and no halogen atoms are detected.
The firing temperature is not particularly limited, but is preferably 800 to 1300C, more preferably 1000 to 1200C.

The content of particles (d) in the antireflection layer is preferably 0.10~0.30g / ^{m 2,} more preferably ^{0.14~0.24g / m 2, 0.16~0.20g / m} 2 Is more preferable.

[Anti-reflection film having irregularities formed by particles (d) on the outermost surface of the anti-reflection layer]
One of the preferred embodiments of the antireflection film of the present invention is an antireflection film having an uneven shape formed by particles (d) on the outermost surface of the antireflection layer. FIG. 4 is a schematic cross-sectional view showing an example of the antireflection film of the present invention in this embodiment.
The uneven shape formed by the particles (d) preferably has a moth-eye structure.
When the antireflection layer contains the particles (d), the surface of the flat portion (film) made of a resin formed by curing the above-described slip agent (a) and the curable compound (b) on the substrate side is It is preferable that the particles (d) protrude from the opposite surface to form projections, and the gaps between the particles (d) form depressions, so that the surface of the antireflection layer has an uneven shape. At this time, the surface of the protruding portion of the particles (d) protruding from the flat portion (film) made of the resin formed by curing the above-mentioned slip agent (a) and the curable compound (b) is: It is preferable that the cured product obtained by curing the above-mentioned slip agent (a) and the curable compound (b) is covered as a film.
And also in this aspect, the antireflection layer of the antireflection film of the present invention has a thickness (S) of 20 nm or less in a direction from the outermost surface opposite to the surface on the substrate side toward the substrate. It includes a cured product of a curable composition containing a slip agent (a), a curable compound (b), and a photopolymerization initiator (c). There is a region where the content of a) is 51% or more. Preferably, the coating covering the surface of the protruding portion of the particles (d) is a region (S) having a thickness of 20 nm or less, and the content of the slip agent (a) in this region (S) is 51% or more. It is preferable to have a region.

(Moss eye structure)
The moth-eye structure is a surface processed with a substance (material) for suppressing light reflection, and refers to a structure having a periodic fine structure pattern. In particular, for the purpose of suppressing the reflection of visible light, it refers to a structure having a fine structure pattern with a period of less than 780 nm. When the period of the fine structure pattern is less than 380 nm, the tint of the reflected light becomes small, which is preferable. Further, it is preferable that the period of the concave and convex shape of the moth-eye structure is 100 nm or more, since light having a wavelength of 380 nm can recognize a fine structure pattern and has excellent antireflection properties. The presence or absence of the moth-eye structure can be confirmed by observing the surface shape with a scanning electron microscope (SEM), an atomic force microscope (AFM), or the like, and examining whether or not the fine structure pattern is formed.

FIG. 2 shows an example of a preferred embodiment of the antireflection film of the present invention.
The anti-reflection film 10 of FIG. 2 has a substrate 1 and an anti-reflection layer 2. The antireflection layer 2 has a moth-eye structure having a concavo-convex shape formed by particles 3 having an average primary particle size of, for example, 150 nm or more and 250 nm or less on the surface opposite to the substrate 1.
The antireflection layer 2 includes particles 3 having an average primary particle size of 150 nm or more and 250 nm or less, and a resin 4.
Although not shown in FIG. 2, another layer may be provided between the base material and the antireflection layer, and a hard coat layer is preferably provided.
The materials of the substrate, the antireflection layer, and the hard coat layer in the antireflection film are the same as those described in the method for producing the antireflection film of the present invention.

The unevenness of the anti-reflection layer of the anti-reflection film is such that B / A, which is the ratio of the distance A between the vertices of the adjacent convex portions and the distance B between the center between the vertices of the adjacent convex portions and the concave portion, is 0. It is preferably 5 or more, more preferably 0.6 or more, and even more preferably 0.7 or more. When B / A is 0.5 or more, the depth of the concave portion becomes large with respect to the distance between the convex portions, and a refractive index gradient layer in which the refractive index changes more gradually from the air to the inside of the antireflection layer is formed. Therefore, the reflectance can be further reduced.
B / A can be controlled by the volume ratio between the resin and the particles in the cured antireflection layer. Therefore, it is important to appropriately design the mixing ratio between the resin and the particles. In addition, the volume ratio of the resin and the particles in the anti-reflection layer is different from the compounding ratio in the anti-reflection layer forming composition by the resin penetrating into the base material or evaporating in the process of producing the moth-eye structure. In some cases, it is important to properly set the matching with the base material.

  It is preferable that the particles forming the convex portions are uniformly spread at an appropriate filling rate. From the above viewpoint, it is preferable that the content of the particles forming the convex portions is adjusted so as to be uniform in the entire antireflection layer. The filling rate can be measured as the area occupancy (particle occupancy) of the particles located on the most surface side when observing the particles forming the projections from the surface by SEM or the like, and is 25% to 84%. , 25-70% is preferred, and 30-65% is more preferred.

  The antireflection layer in the present invention reflects that a plurality of particles (d) do not exist in a direction perpendicular to the surface of the substrate (that is, no particles (d) overlap each other in a direction perpendicular to the surface of the substrate). The rate and haze are low and are preferable.

[Production method of antireflection film]
The method for producing the antireflection film of the present invention is not particularly limited. Examples of the method for producing an antireflection film in which the antireflection layer contains the particles (d) described above include:
On the substrate,
A composition containing a slipping agent (a), a curable compound (b), a photopolymerization initiator (c), particles (d), and a solvent is applied, and the solvent is volatilized. A step (1) of providing a layer (A) having a thickness of at least 0.8 times the average primary particle diameter of the particles (d);
A step (2) of curing a part of the curable compound (b) in the layer (A) to obtain a cured compound (bc);
A part of the compound selected from the group consisting of the curable compound (b) and the compound (bc) in the layer (A) is made to penetrate or volatilize into the substrate by heating, and the layer side of the layer (A) (3) forming an uneven shape made of particles (d) on the surface opposite to the surface of
(C) curing the compound selected from the group consisting of the curable compound (b) and the compound (bc) remaining in the layer (A) to form an antireflection layer;
In this order, the method for producing an antireflection film is preferable.
FIG. 1 is a schematic view showing an example of the method for producing the antireflection film of the present invention.

[Step (1)]
In the step (1), as shown in FIG. 1 (1), a slip agent (a), a curable compound (b), a photopolymerization initiator (c), Fine particles (d) having an average primary particle diameter of 250 nm or less (reference numeral 3 in FIG. 1) and a composition containing a solvent are applied, and the solvent is volatilized. This is a step of providing a layer (A) (reference numeral 4 in FIG. 1) having a thickness of 0.8 times or more the average primary particle size of (d).

  The slip agent (a), the curable compound (b), the photopolymerization initiator (c), and the particles (d) used in the above step (1) are as described above.

<Solvent>
It is preferable to select a solvent having a polarity close to that of the particles (d) from the viewpoint of improving dispersibility. Specifically, for example, when the particles (d) are metal oxide particles, an alcohol-based solvent is preferable, and examples thereof include methanol, ethanol, 2-propanol, 1-propanol, and butanol. Further, for example, in the case of metal resin particles obtained by subjecting the particles (d) to hydrophobic surface modification, a solvent such as a ketone, ester, carbonate, alkane, or aromatic solvent is preferable, and methyl ethyl ketone (MEK), carbonate Examples thereof include dimethyl, methyl acetate, acetone, methylene chloride, and cyclohexanone. These solvents may be used as a mixture of two or more kinds as long as the dispersibility is not significantly deteriorated.

  The composition (the composition for forming an anti-reflection layer) used in the step (1) includes components other than a slip agent (a), a curable compound (b), a photopolymerization initiator (c), particles (d), and a solvent. May be contained, for example, a dispersant for the particles (d), a leveling agent, an antifouling agent, and the like.

  The method for applying the composition on a substrate is not particularly limited, and a known method can be used. Examples include a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, and a die coating method.

The content of particles (d) in the layer (A) in step (1) is preferably 0.10~0.30g / ^{m 2,} more preferably 0.14~0.24g / ^{m 2,} 0.16 More preferably, it is で 0.20 g / m ² . 0.10 g / m ² or more in the more easily improved antireflection properties since it protrusions numerous forms of moth-eye structure as long, if it is 0.30 g / m ² or less, hardly occurs agglomeration in the liquid, moth It is easy to form the structure well.

<Dispersant for particles (d)>
The dispersant for the particles (d) can make it easier to arrange the particles (d) uniformly by reducing the cohesive force between the particles. The dispersant is not particularly limited, but is preferably an anionic compound such as a sulfate or a phosphate, a cationic compound such as an aliphatic amine salt or a quaternary ammonium salt, a nonionic compound, or a polymer compound. And a high molecular weight compound are more preferable since the degree of freedom in selecting each of the steric repulsion group and the steric repulsion group is high. Commercial products can also be used as the dispersant. For example, BYK Japan made of (stock) DISPERBYK160, DISPERBYK161, DISPERBYK162, DISPERBYK163, DISPERBYK164, DISPERBYK166, DISPERBYK167, DISPERBYK171, DISPERBYK180, DISPERBYK182, DISPERBYK2000, DISPERBYK2001, DISPERBYK2164, Bykumen, BYK-2009, BYK-P104, BYK-P104S, BYK-220S, Anti-Terra 203, Anti-Terra 204, Anti-Terra 205 (all trade names) and the like.

  In the present invention, a functional layer may be provided on the substrate before the step (1). When a functional layer is provided on a substrate, a laminate of the functional layer and the substrate is referred to as a “substrate”. When the functional layer is provided on the surface of the base material on which the layer (A) is to be provided, the layer (A) is provided on the functional layer in step (1), and the subsequent steps are performed. A hard coat layer is preferable as the functional layer.

  In the present invention, the substrate is preferably a substrate having a hard coat layer (also referred to as a “substrate with a hard coat layer”), and the composition in the above step (1) is applied on the hard coat layer. Is preferred.

<Layer (A)>
In the layer (A), the solvent is volatilized from the composition for forming an antireflection layer applied on the base material, and the thickness of the portion where the particles (d) are not present is set to be 0.1 mm of the average primary particle size of the particles (d). This is a layer having a thickness of 8 times or more, and contains a slip agent (a), a curable compound (b), a photopolymerization initiator (c), and particles (d).
The layer (A) is a layer which will later become an antireflection layer by the production method of the present invention.
The curable compound (b) contained in the layer (A) becomes a resin when cured. This resin forms the concave and convex portions of the antireflection layer.
The particles (d) contained in the layer (A) protrude from the surface of the resin film in the obtained antireflection film, and form projections and depressions.
In the present invention, since the slipping agent (a) also has a crosslinking group, the slipping agent (a) is cured with each other or together with the curable compound (b) to form a cured product, which is present in the concave portion. As described above, the cured product is preferably present in the coating covering the surface of the particles (d) forming the projections.
Since the layer (A) is partially cured in the step (2), the components contained before and after the curing are different. I do. Before and after steps (3) and (4), it is also referred to as layer (A).

  In step (1), it is preferable that a plurality of particles (d) do not exist in a direction perpendicular to the surface of the substrate in the applied layer (A). Here, that a plurality of particles (d) do not exist in the direction orthogonal to the surface of the base material means that the surface of the base material is observed when three fields of 10 μm × 10 μm are observed with a scanning electron microscope (SEM) in three fields. The ratio of the number of particles (d) which do not exist in a plurality in the direction orthogonal to each other (is present alone) is 80% or more, and preferably 95% or more.

  In the step (1), the thickness of the portion of the layer (A) where the particles (d) are not present is at least 0.8 times, preferably at least 0.8 times the average primary particle size of the particles (d). 2.0 times or less, more preferably 0.9 times or more and 1.5 times or less, particularly preferably 1.0 times or more and 1.2 times or less. This makes it difficult for the particles (d) to agglomerate, and a desirable uneven shape is easily obtained.

[Step (2)]
In the step (2), as shown in FIG. 1 (2), a part of the curable compound (b) in the layer (A) 4 in the step (1) is cured, and the cured compound (bc) is removed. This is the step of obtaining.
In step (2), the slip agent (a) may or may not be cured.
The compound (bc) may include a compound obtained by curing the slip agent (a) and the curable compound (b).
By curing a part of the curable compound (b) in the step (2), it is possible to make the particles (d) 3 hard to move and to suppress the particles (d) from aggregating.
Curing a part of the curable compound (b) means curing not a part but a part of the curable compound (b). By curing only a part of the curable compound (b) in the step (2), the uncured curable compound (b) can be penetrated into the substrate by heating in the step (3) described below, The thickness of the portion of the layer (A) where the particles (d) are not present can be reduced, and the particles (d) can be protruded to form a good uneven shape (moth-eye structure).

It is preferable that the curable compound (b) is a photocurable compound, and that part of the curable compound (b) is cured by irradiating light (preferably ultraviolet light) in step (2).
In the step (2), a condition for curing a part of the curable compound (b) is as follows. Then, when cured, it is preferable that the curing rate is 2 to 20%, more preferably the curing rate is 3 to 15%, and the curing rate is 5 to 10%. More preferably, the condition is satisfied.

The curing rate is
{(1−number of remaining polymerizable functional groups after curing) / number of polymerizable functional groups before curing} × 100%
And is measured by the following method.
The polymerizable functional group is a group having a polymerizable carbon-carbon unsaturated double bond.
More specifically, the curable compound itself before curing is measured by KBr-IR using NICOLET 6700 FT-IR of Thermo electron corporation, and the peak (1660-1800 cm ^-1 ) area of the carbonyl group and the polymerizable carbon- The peak height of the carbon-unsaturated double bond (808 cm ^-1 ) was determined, and the peak of the polymerizable carbon-carbon unsaturated double bond with respect to the carbonyl group peak area was similarly determined from the single reflection IR measurement after curing. The curing rate was calculated by comparing before and after irradiation with ultraviolet rays. When calculating hardening rate here is normalized measurement depth at 808cm ^-1 821nm, a depth of 1660-1800Cm ^-1 as 384 nm.

In the step (2), it is preferable to irradiate ultraviolet rays at a dose of 1 to 90 mJ / cm ² , more preferably at a dose of 1.2 to 40 mJ / cm ² , and 1.5 to 10 mJ / cm ^2. It is more preferable to irradiate at an irradiation amount of ² .

  In the step (2), it is preferable that a part of the curable compound (b) is cured by irradiating ultraviolet rays from the side opposite to the side having the layer (A) of the substrate. This makes it possible to harden particularly the region of the layer (A) on the substrate side, and it is easy to form a convex portion due to the particles (d) in a subsequent step while keeping the particles (d) stationary.

  Step (2) is preferably performed in an environment with an oxygen concentration of 0.1 to 5.0% by volume, more preferably in an environment with an oxygen concentration of 0.5 to 1.0% by volume. . When the oxygen concentration is in the above range, the region on the base material side of the layer (A) can be particularly hardened.

The compound (bc) is a cured product of the curable compound (b).
The molecular weight of compound (bc) is not particularly limited. Further, the compound (bc) may have an unreacted polymerizable functional group.

[Step (3)]
In the step (3), as shown in FIG. 1 (3), a part of a compound selected from the group consisting of the curable compound (b) and the compound (bc) in the layer (A) 4 is heated to thereby form a part. This is a step of forming a concavo-convex shape composed of particles (d) 3 on the surface of the layer (A) opposite to the substrate by infiltrating or volatilizing the substrate. Here, the curable compound (b) which is made to penetrate or volatilize into the substrate by heating is preferably a curable compound (b) which was not cured in the step (2).
In step (3), it is preferable that the slip agent (a) does not penetrate into the base material and does not volatilize.

  Step (3) of allowing a part of a compound selected from the group consisting of the curable compound (b) and the compound (bc) to penetrate into a substrate (or a functional layer if the substrate has a functional layer) )), It is preferable to heat the laminate having the substrate and the layer (A). By heating, a part of the compound selected from the group consisting of the curable compound (b) and the compound (bc) can be effectively penetrated into the base material. The heating temperature is preferably lower than the glass transition temperature of the substrate, specifically, preferably from 60 to 150 ° C, and more preferably from 80 to 120 ° C.

When the step (3) is a step of volatilizing a part of the compound selected from the group consisting of the curable compound (b) and the compound (bc), the curable compound (b) has a boiling point at 1 atm. Those having a molecular weight of 150 ° C. or less are preferred, and those having a molecular weight of 300 or less are preferred. Specifically, Blemmer GMR is preferred.
One atm is 101325 Pa.

  In the step (3), a part of the compound selected from the group consisting of the curable compound (b) and the compound (bc) in the layer (A) is infiltrated into the substrate by heating or volatilized. An uneven shape is formed on the surface of the layer (A). The convex portion of the uneven shape is a particle (d), and the concave portion is a compound selected from the group consisting of a slip agent (a), a curable compound (b) and a compound (bc) remaining in the layer (A). is there.

[Step (4)]
Step (4) is selected from the group consisting of a slip agent (a), a curable compound (b) and a compound (bc) remaining in the layer (A) as shown in (4) of FIG. This is a step of curing the compound.
The curing in the step (4) is preferably photocuring, and more preferably curing by ultraviolet irradiation. The irradiation amount of the ultraviolet rays is preferably 300 mJ / cm ² or more, and the curing is preferably performed in an environment having an oxygen concentration of 0.01 vol% or less.
In the step (4), a compound selected from the group consisting of the slip agent (a), the curable compound (b) and the compound (bc) remaining in the layer (A) is cured to obtain a resin, Is formed as a concave portion, and an anti-reflection layer having a moth-eye structure having a concave-convex shape having particles (d) 3 projecting from the resin as convex portions is formed.
After the step (4), the average surface roughness Ra is preferably 15 nm or more, more preferably 30 nm or more, and most preferably 40 nm or more.

[Step (E1) and Step (E2)]
In the present invention, between step (1) and step (2), between step (2) and step (3), or between step (3) and step (4),
A step (E1) of providing a layer (E) containing a compound (e) incompatible with the curable compound (b) on the surface of the layer (A) opposite to the substrate-side surface;
It is preferable to include a step (E2) of removing the layer (E) after the step (2), the step (3), or the step (4) performed subsequent to the step (E1).
Step (E1) preferably has between step (1) and step (3), and more preferably has between step (2) and step (3).
The step (E2) is preferably provided after the step (4).

<Layer (E)>
The layer (E) contains a compound (e) incompatible with the curable compound (b) (hereinafter, also simply referred to as “compound (e)”).
The layer (E) is preferably provided to prevent the particles (d) in the layer (A) from aggregating, and is preferably removed finally.
The fact that the compound (e) is not compatible with the curable compound (b) means that the compound (e) is mixed with 5% by mass of the curable compound (b) at 25 ° C. and an insoluble material remains when the mixture is stirred. It is.
Further, the compound (e) is preferably a compound that is not cured by heat. By making the compound (e) a compound that is not cured by heat, even if a heating process is included before the removal of the compound (e) in the production method of the present invention, a moth-eye structure is easily formed by the particles (d), which is preferable. .
In particular, when the layer (E) is provided before the step (3), the boiling point of the compound (e) contained in the layer (E) is preferably equal to or higher than the heating temperature in the step (3).

  When the layer (E) is provided by coating as the compound (e), it is preferably an oil component that is liquid at 50 ° C., and is a silicone oil component, a hydrocarbon oil component, an ester oil component, a natural animal and vegetable oil and fat. More preferably, it is a semi-synthetic fat, a higher fatty acid, a higher alcohol, or a fluorinated oil component.

≪Silicon-based oil component≫
The silicone-based oil component may be any of a solid, semi-solid, and liquid. As the silicone oil component, for example, silicone oil, silicone surfactant, silicone resin, silicone wax, and silicone gelling agent can be used.

  Examples of the silicone oil include dimethylpolysiloxane (for example, KF96 series manufactured by Shin-Etsu Chemical Co., Ltd.), tristrimethylsiloxymethylsilane, caprylylmethicone, phenyltrimethicone, tetrakistrimethylsiloxysilane, methylphenylpolysiloxane, methylhexylpolysiloxane, Low- to high-viscosity linear or branched organopolysiloxanes such as methylhydrogenpolysiloxane and dimethylsiloxane-methylphenylsiloxane copolymer; octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane Cyclic organopolysiloxanes such as tetramethyltetrahydrogencyclotetrasiloxane and tetramethyltetraphenylcyclotetrasiloxane; Pyrolidone-modified organopolysiloxane; Pyrrolidonecarboxylic acid-modified organopolysiloxane; Highly polymerized gum-like dimethylpolysiloxane, gum-like amino-modified organopolysiloxane, gum-like dimethylsiloxane-methylphenylsiloxane copolymer And a cyclic organopolysiloxane solution of silicone gum or rubber; trimethylsiloxysilicic acid, a cyclic siloxane solution of trimethylsiloxysilicic acid (eg, Shin-Etsu Chemical: KF-7312J, etc.); Alkoxy-modified silicones; higher fatty acid-modified silicones; alkyl-modified silicones; long-chain alkyl-modified silicones; amino acid-modified silicones; fluorine-modified silicones; It is.

  Examples of the silicone-based surfactant include linear or branched polyoxyethylene-modified organopolysiloxane, linear or branched polyoxyethylene polyoxypropylene-modified organopolysiloxane, and linear or branched polyoxyethylene / alkyl. Modified organopolysiloxane, linear or branched polyoxyethylene polyoxypropylene / alkyl co-modified organopolysiloxane, linear or branched polyglycerin-modified organopolysiloxane, linear or branched polyglycerin / alkyl co-modified organopolysiloxane (Specific examples include Shin-Etsu Chemical industrial silicone emulsifiers: KF-6011, 6043, 6028, 6038, 6100, 6104, 6105, etc.). A state in which polyoxyethylene-modified partially crosslinked organopolysiloxane, polyglycerin-modified partially crosslinked polyorganopolysiloxane and the like coexist with other oily components (for example, KSG series; KSG-210, 710, manufactured by Shin-Etsu Chemical Co., Ltd.) , 310, 320, 330, 340, 320Z, 350Z, 810, 820, 830, 840, 820Z, 850Z, etc.).

Examples of the silicone resin include an acrylic silicone resin composed of an acrylic / silicone graft copolymer, an acrylic / silicone block copolymer, etc. (Specific examples include Shin-Etsu Chemical's acrylic / silicone graft copolymer. Cyclic organopolysiloxane solution: KP-545 and the like). In addition, an acrylic silicone resin containing at least one selected from a pyrrolidone moiety, a long-chain alkyl moiety, a polyoxyalkylene moiety, a fluoroalkyl moiety, and an anionic moiety such as a carboxylic acid in the molecule can also be used. Further the silicone resin, R ⁸ ₃ SiO _0.5 units and a resin composed of a SiO ₂ units, R ⁸ ₃ SiO _0.5 units and R ⁸ ₂ resin composed of a SiO units and SiO ₂ units, R ⁸ ₃ SiO resin composed of _0.5 units and R ⁸ SiO _1.5 units, a resin composed of a R ⁸ ₃ SiO _0.5 units and R ⁸ ₂ SiO units and R ⁸ SiO _1.5 units, and, R ⁸ ₃ SiO _0.5 units, R ⁸ ₂ SiO units, is preferably a network silicone compound comprising at least one resin composed of R ⁸ SiO _1.5 units and SiO ₂ units. R ⁸ in the formula is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms. Further, a silicone network compound containing at least one selected from a pyrrolidone portion, a long-chain alkyl portion, a polyoxyalkylene portion, a polyglycerin portion, a fluoroalkyl portion, and an amino portion in a molecule can also be used.

  Examples of the silicone wax include an acrylic silicone wax composed of an acrylic / silicone graft copolymer, an acrylic / silicone block copolymer, etc. (Specific examples include Shin-Etsu Chemical's acrylic / silicone graft copolymer. Cyclic organopolysiloxane solution: KP-561P, 562P, etc.). An acrylic silicone wax containing at least one selected from a pyrrolidone portion, a long-chain alkyl portion, a polyoxyalkylene portion, a fluoroalkyl portion, and an anionic portion such as a carboxylic acid in the molecule can also be used. The silicone wax is preferably a polylactone-modified polysiloxane to which a polylactone, which is a ring-opening polymer of a lactone compound having five or more ring members, is bonded. Further, the silicone wax is obtained by subjecting an olefin wax having an unsaturated group consisting of an α-olefin and a diene to an addition reaction with an organohydrogenpolysiloxane having one or more SiH bonds per molecule. It is an olefin wax. The α-olefin is preferably an α-olefin having 2 to 12 carbon atoms such as ethylene, propylene, 1-butene, 1-hexene, and 4-methyl 1-pentene. As the diene, butadiene, isoprene, 1,4 -Hexadiene, vinyl norbornene, ethylidene norbornene, dicyclopentadiene and the like are preferred. As the organohydrogenpolysiloxane having a SiH bond, those having a linear structure and those having a siloxane branched structure can be used.

  Examples of the silicone-based gelling agent include non-modified or modified moieties such as non-modified partially crosslinked organopolysiloxane, alkyl-modified partially crosslinked organopolysiloxane, and silicone branched alkyl-modified partially crosslinked organopolysiloxane. A gel mixture containing a gelling component such as a cross-linked organopolysiloxane and various oil components such as cyclopentasiloxane, dimethicone, mineral oil, isododecane, trioctanoin, and squalane is exemplified. The gel mixture contains the gelling component and the oil component together. Examples of the gel mixture include KSG series (trade name) manufactured by Shin-Etsu Chemical Co., Ltd., particularly, KSG-15, 16, 41, 42, 43, 44, 042Z, and 045Z (all trade names).

≪Hydraulic oil component≫
Examples of the hydrocarbon-based oil component include liquid paraffin, light liquid isoparaffin, heavy liquid isoparaffin, petrolatum, n-paraffin, isoparaffin, isododecane, isohexadecane, polyisobutylene, hydrogenated polyisobutylene, polybutene, ozokerite, ceresin, and microcrystalline wax. , Paraffin wax, polyethylene wax, polyethylene / polypropylene wax, squalane, squalene, pristane, polyisoprene, wax and the like.

≪Ester-based oil component≫
Examples of ester-based oily components include hexyldecyl octoate, cetyl octoate, isopropyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, oleyl oleate, decyl oleate, octyl dodecyl myristate, dimethyl Hexyldecyl octanoate, cetyl lactate, myristyl lactate, diethyl phthalate, dibutyl phthalate, lanolin acetate, ethylene glycol monostearate, propylene glycol monostearate, propylene glycol dioleate, glyceryl monostearate, glyceryl monooleate, tri Glyceryl 2-ethylhexanoate, trimethylolpropane tri-2-ethylhexanoate, ditrimethylolpropane triethylhexanoate, (a (Stearic acid / sebacic acid) ditrimethylolpropane, trimethylolpropane trioctanoate, trimethylolpropane triisostearate, diisopropyl adipate, diisobutyl adipate, 2-hexyldecyl adipate, di-2-heptylundecyl adipate, malic acid Diisostearyl, hydrogenated castor oil monoisostearate, N-alkyl glycol monoisostearate, octyldodecyl isostearate, isopropyl isostearate, isocetyl isostearate, ethylene glycol di-2-ethylhexanoate, cetyl 2-ethylhexanoate, Pentaerythritol tetra-2-ethylhexanoate, octyldodecyl gum ester, ethyl oleate, octyldodecyl oleate, neopepic dicaprate Tyl glycol, triethyl citrate, 2-ethylhexyl succinate, dioctyl succinate, isocetyl stearate, diisopropyl sebacate, di-2-ethylhexyl sebacate, diethyl sebacate, dioctyl sebacate, dibutyl octyl sebacate, cetyl parimitic acid, Octyldodecyl palmitate, octyl palmitate, 2-ethylhexyl palmitate, 2-hexyldecyl palmitate, 2-heptylundecyl palmitate, cholesteryl 12-hydroxystearylate, dipentaerythritol fatty acid ester, 2-hexyldecyl myristate, Ethyl laurate, N-lauroyl-L-glutamic acid-2-octyldodecyl ester, N-lauroyl-L-glutamic acid di (cholesteryl / behenyl / o Octyldodecyl), di-N-lauroyl-L-glutamate (cholesteryl / octyldodecyl), di-N-lauroyl-L-glutamate (phytosteryl / behenyl / octyldodecyl), di-N-lauroyl-L-glutamate (phytosteryl / octyldodecyl), N-lauroyl sarcosine isopropyl, diisostearyl malate, neopentyl glycol dioctanoate, isodecyl neopentanoate, isotridecyl neopentanoate, isostearyl neopentanoate, isononyl isononanoate, isotridecyl isononanoate, octyl isononanoate, isotridecyl isononanoate, diethyl dineopentate Pentanediol, methylpentanediol dinepentanoate, octyldodecyl neodecanoate, 2-butyl dioctanoate -Ethyl-1,3-propanediol, pentaerythrityl tetraoctanoate, hydrogenated rosin pentaerythrityl, pentaerythrityl triethylhexanoate, dipentaerythrityl (hydroxystearic acid / stearic acid / rosinic acid), polyglyceryl tetraisostearate, nona Polyglyceryl-10 isostearate, polyglyceryl-8 deca (erucic acid / isostearic acid / ricinoleic acid), diglyceryl oligoester (hexyldecanoic acid / sebacic acid), glycol distearate (ethylene glycol distearate), diisopropyl dimer dilinoleate, die Diisostearyl dimeryl linoleate, di (distearyl dimethyaryl) / phytosteryl, dimer dilinoleic acid (phytosteryl / beheni) ), Dimer dilinoleic acid (phytosteryl / isostearyl / cetyl / stearyl / behenyl), dimer dilinoleyl dimer dilinoleate, dimer dilinoleyl diisostearate, hydrogenated rosin condensate of dimer dilinoleyl, hardened dimer dilinoleic acid Castor oil, hydroxyalkyl dimer dilinoleyl ether, glyceryl triisooctanoate, glyceryl triisostearate, glyceryl trimyristate, glyceryl triisopalmitate, glyceryl trioctanoate, glyceryl trioleate, glyceryl diisostearate, tri (caprylic acid / Glyceryl (capric acid), glyceryl tri (caprylic / capric / myristic / stearic), hydrogenated rosin triglyceride (hydrogenated ester gum), rosinto Liglyceride (ester gum), glyceryl eicosantioate behenate, glyceryl di-2-heptylundecanoate, diglyceryl isostearate myristate, cholesteryl acetate, cholesteryl nonanoate, cholesteryl stearate, cholesteryl isostearate, cholesteryl oleate, 12- Cholesteryl hydroxystearate, cholesteryl macadamia nut oil fatty acid, phytosteryl macadamia nut oil fatty acid, phytosteryl isostearate, soft lanolin fatty acid cholesteryl, hard lanolin fatty acid cholesteryl, long chain branched cholesteryl cholesteryl, long chain α-hydroxy fatty acid cholesteryl, ricinoline ricinoleate fatty acid Octyldodecyl, octyldodecyl erucate, hydrogenated castor oil isostearate Avocado oil fatty acid ethyl, isopropyl lanolate, and the like.

≪Natural animal and vegetable fats and oils and semi-synthetic fats≫
As natural animal and vegetable oils and fats and semi-synthetic oils, avocado oil, linseed oil, almond oil, ibotaro, eno oil, olive oil, cocoa butter, kapok wax, kaya oil, carnauba wax, liver oil, candelilla wax, tallow, beef tallow, cow Bone fat, hardened beef tallow, ginger oil, spermaceti, hardened oil, wheat germ oil, sesame oil, rice germ oil, rice bran oil, sugar cane wax, sasanqua oil, safflower oil, shea butter, cinnamon oil, cinnamon oil, jojoba wax, Olive squalane, shellac wax, turtle oil, soybean oil, teaseed oil, camellia oil, evening primrose oil, corn oil, lard, rapeseed oil, Japanese kiri oil, nukarou, germ oil, horse fat, persic oil, palm oil, palm kernel Oil, castor oil, hydrogenated castor oil, castor oil fatty acid methyl ester, sunflower oil, grape oil, bayberry wax, jojoba oil Hydrogenated jojoba ester, macadamia nut oil, beeswax, mink oil, cottonseed oil, cotton wax, mokuro, mokuro kernel oil, montan wax, coconut oil, hydrogenated coconut oil, tricoconut oil fatty acid glyceride, sheep fat, peanut oil, lanolin, liquid lanolin, reduction Lanolin, lanolin alcohol, hard lanolin, lanolin acetate, isopropyl lanolin fatty acid, POE (polyoxyethylene) lanolin alcohol ether, POE lanolin alcohol acetate, lanolin fatty acid polyethylene glycol, hydrogenated lanolin alcohol ether of POE, egg yolk oil and the like.

≪Higher fatty acids≫
As higher fatty acids, for example, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, undecylenic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA), Isostearic acid, 12-hydroxystearic acid and the like can be mentioned.

≪Higher alcohol≫
As higher alcohols, for example, lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, behenyl alcohol, hexadecyl alcohol, oleyl alcohol, isostearyl alcohol, hexyldecanol, octyldodecanol, cetostearyl alcohol, 2-decyltetradecyl Examples thereof include knol, cholesterol, sitosterol, phytosterol, lanosterol, POE cholesterol ether, monostearyl glycerin ether (bacyl alcohol), and monooleyl glyceryl ether (serakyl alcohol).

≪Fluorine oil component 性
Examples of the fluorinated oil component include perfluoropolyether, perfluorodecalin, and perfluorooctane.

  The compound (e) is preferably a liquid at 50 ° C., and more preferably a liquid at 25 ° C., from the viewpoint of suppressing aggregation of particles forming a moth-eye structure and reducing the cloudiness of the antireflection film. Further, it is preferable that at least one of the compounds (e) has a boiling point of 110 ° C. or higher. When the boiling point is 110 ° C. or higher, it is difficult to volatilize at room temperature, and the layer (A) can be present as the layer (E) until the curing of the layer (A) is completed.

It is preferable that kinematic viscosity at 25 ° C. of compounds having a boiling point of 110 ° C. or higher from the viewpoint (e) is ^{0.1mm 2 / s~100000mm 2 / s,} 0.1mm 2 / s~10000mm 2 / s is more ^preferable, and it is most preferably a 0.1mm ² / s~100mm 2 / s.

  Compound (e) may be used alone or in combination of two or more.

  The content of the compound (e) in the layer (E) is preferably from 50 to 100% by mass, more preferably from 70 to 100% by mass, even more preferably from 90 to 100% by mass based on the total mass of the layer (E).

In the step (E2), a method for removing the layer (E) is not particularly limited, but a method using a solvent that dissolves the compound (e) without dissolving the substrate and the cured layer (A), a method using the compound (e) A method in which the compound (e) is volatilized by heating at a temperature higher than the boiling point of the compound (e), a method in which the compound (e) is dissolved in an alkaline solution, and the like are preferable.
The solvent for dissolving the compound (e) without dissolving the substrate and the cured layer (A) is not particularly limited. When the substrate is triacetyl cellulose, methanol, ethanol, 2-propanol, -Alcohol solvents such as propanol, n-butanol, isobutanol, diacetone alcohol and methoxypropanol; ketone solvents such as methyl isobutyl ketone and methyl butyl ketone; aromatic solvents such as toluene and xylene; cyclohexane and propylene glycol monomethyl Ether acetate and the like are preferred. These solvents may be used as a mixture of two or more.

  The heating temperature for volatilizing the compound (e) is preferably lower than the glass transition temperature of the base material and higher than the boiling point of the compound (e), and specifically, 60 to 180 ° C. Preferably, the temperature is more preferably 80 to 130 ° C.

  As a solution when dissolving with an alkali solution, it is preferable to use an aqueous solution of sodium hydroxide or potassium hydroxide.

<Other layers>
As described above, another layer may be formed between the substrate and the layer (A). In this case, a laminate composed of the base material and other layers is referred to as a base material. Examples of the other layers include various functional layers, and a hard coat layer is particularly preferable.

(Hard coat layer)
The hard coat layer is preferably formed by a crosslinking reaction of a curable compound or a polymerization reaction. For example, for the hard coat layer, a composition for forming a hard coat layer containing a polyfunctional monomer and / or a polyfunctional oligomer is applied on a substrate, and a crosslinking reaction or a polymerization reaction of the polyfunctional monomer or the polyfunctional oligomer is performed. It is preferable to form with.
The functional group (polymerizable group) of the polyfunctional monomer or polyfunctional oligomer is preferably a light, electron beam, or radiation polymerizable group, and among them, a photo (preferably, ultraviolet) polymerizable functional group is preferable.
Examples of the photopolymerizable functional group include unsaturated polymerizable functional groups such as a (meth) acryloyl group, a vinyl group, a styryl group, and an allyl group. Among them, a (meth) acryloyl group is preferable.

  Regarding the curable compound in the hard coat layer, the description of [0021] to [0027] of JP-A-2014-240956 can be referred to in the present invention.

The thickness of the hard coat layer is usually about 0.6 μm to 50 μm, and preferably 5 μm to 20 μm, from the viewpoint of imparting sufficient durability and impact resistance to the film.
Further, the strength of the hard coat layer is preferably H or more, more preferably 2H or more, in a pencil hardness test. Furthermore, in a Taber test according to JIS K 5600-5-4 (1999), it is preferable that the wear amount of the test piece before and after the test is smaller.
By providing the hard coat layer, for example, when a pencil hardness test is performed, it is possible to further prevent the plastic substrate (such as a cellulose acylate substrate or an acrylic substrate) from being damaged.

When the hard coat layer contains a curable compound, it is preferable that the curable compound of the hard coat layer is not cured in the step (2). Thereby, in the step (3), a part of the compound selected from the group consisting of the curable compound (b) and the compound (bc) in the layer (A) can be easily penetrated into the hard coat layer.
In order to prevent the curable compound of the hard coat layer from being cured in the step (2), the following embodiments can be mentioned. In the following embodiments, the curable compound contained in the composition for forming a hard coat layer and the composition for forming an antireflection layer is a photocurable compound. Further, in the step (3), a part of the curable compound (b) of the layer (A) is made to penetrate into the hard coat layer by heating.

  The hard coat layer is obtained by curing the composition for a hard coat layer containing a curable compound, and the amount of increase in the cure rate due to the curing in the step (2) is preferably less than 5%, more preferably less than 3%. , Less than 1.5% is most preferred.

  When an antireflection layer is provided on a substrate having a hard coat layer, the following embodiments 1 to 4 are preferable.

Embodiment 1: An embodiment in which the composition for forming a hard coat layer contains a photo-radical polymerization initiator A and an embodiment in which the composition for forming an anti-reflection layer contains a photo-radical polymerization initiator A In this embodiment, a hard coat layer is formed on a substrate. The composition for forming is applied and irradiated with ultraviolet rays at a relatively low exposure dose to cause a part of the photoradical polymerization initiator A to be cleaved to generate a radical and a part to not be cleaved. At this time, a part of the curable compound of the hard coat layer is cured. Thereafter, a composition for forming an antireflection layer is applied on the hard coat layer, and a part of the curable compound (b) is cured in step (2). Then, in the step (3), a part of the uncured curable compound (b) is made to penetrate into the hard coat layer, and in the step (4), the hard curable compound of the hard coat layer and the uncured curable compound are irradiated with ultraviolet rays. The compound (b) is cured.

Aspect 2: The composition for forming a hard coat layer contains a photo-radical polymerization initiator A and a thermal radical polymerization initiator that generates a radical by heat, and the composition for forming an anti-reflection layer contains the photo-radical polymerization initiator A. In this embodiment, the composition for forming a hard coat layer is applied on a substrate, and the composition is irradiated with ultraviolet rays at a relatively high exposure dose, and almost all of the photoradical polymerization initiator A is cleaved to generate radicals. At this time, a part of the curable compound of the hard coat layer is cured. Thereafter, a composition for forming an antireflection layer is applied on the hard coat layer, and a part of the curable compound (b) is cured in step (2). Thereafter, in the step (3), a part of the uncured curable compound (b) penetrates into the hard coat layer, and in the step (4), ultraviolet rays are irradiated to cure the uncured curable compound (b). Then, after heating, the thermal polymerization initiator in the hard coat layer is cleaved to generate radicals to cure the curable compound. The temperature for generating radicals from the thermal radical polymerization initiator is preferably higher than the permeation temperature in step (3), for example, preferably 100 to 180 ° C. As the thermal radical polymerization initiator, VF-096, VAm-11 (all manufactured by Wako Pure Chemical Industries, Ltd.) and the like can be suitably used.

Embodiment 3: The composition for forming a hard coat layer contains a photo-radical polymerization initiator A that generates radicals by irradiating ultraviolet rays using a lamp A, and the composition for forming an anti-reflection layer contains a photo-radical polymerization initiator A And an embodiment containing a photo-radical polymerization initiator B that generates radicals by irradiating ultraviolet rays using a lamp B. In this embodiment, a composition for forming a hard coat layer is applied on a base material, and the lamp A is used. Irradiation with ultraviolet light at a relatively low exposure dose consumes a part of the photoradical polymerization initiator A and leaves a part. At this time, a part of the curable compound of the hard coat layer is cured. Thereafter, the composition for forming an anti-reflection layer is applied on the hard coat layer, and in step (2), ultraviolet rays are irradiated using a lamp B to partially cure the curable compound (b). Then, in the step (3), a part of the uncured curable compound (b) is penetrated into the hard coat layer, and in the step (4), ultraviolet light is irradiated using the lamp A, and the curable compound of the hard coat layer is removed. The uncured curable compound (b) is cured. Examples of the combination of the lamp A and the photoradical polymerization initiator A include a high-pressure mercury lamp having a strong specific wavelength spectrum, Irgacure 907, and Irgacure 369. Examples of the combination of the lamp B and the radical photopolymerization initiator B include a metal halide lamp having a relatively broad wavelength spectrum, Irgacure 127, and Irgacure 184. It is also preferable to shift the cleavage wavelength of the initiator using UV-LED light having a relatively long wavelength.

Aspect 4: An embodiment in which the composition for forming a hard coat layer contains a thermal radical polymerization initiator that generates radicals by heat, and a composition for forming an antireflection layer contains an optical radical polymerization initiator A. The composition for forming a hard coat layer is applied thereon, and a little heat is applied to consume a part of the thermal radical polymerization initiator and leave a part. At this time, a part of the curable compound of the hard coat layer is cured. Thereafter, a composition for forming an anti-reflection layer is applied on the hard coat layer, and ultraviolet rays are irradiated in step (2) to cure a part of the curable compound (b). Thereafter, in the step (3), a part of the uncured curable compound (b) penetrates into the hard coat layer, and in the step (4), ultraviolet rays are irradiated to cure the uncured curable compound (b). After that, heating is performed to generate radicals by the thermal radical polymerization initiator in the hard coat layer, thereby curing the curable compound. The temperature for generating radicals from the thermal radical polymerization initiator is preferably higher than the permeation temperature in step (3), for example, preferably 100 to 180 ° C.

The antireflection film produced by the production method of the present invention can be suitably used as a polarizing plate protective film.
The polarizing plate protective film using the antireflection film manufactured by the manufacturing method of the present invention can be bonded to a polarizer to form a polarizing plate, and can be suitably used for a liquid crystal display device and the like.

  Hereinafter, the present invention will be described more specifically with reference to examples. Materials, reagents, substance amounts and their ratios, operations, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples.

(Preparation of substrate 1)

(Degree of acetyl substitution)
The acetyl substitution degree of cellulose acylate was measured by the following method.
The acetyl substitution degree was measured according to ASTM D-817-91.

(Preparation of cellulose acylate solution for air layer)
The following composition was put into a mixing tank, and stirred while heating to dissolve each component to prepare a cellulose acylate solution for an air layer.

Composition of cellulose acylate solution for air layer 100 parts by mass of cellulose acylate (acetyl substitution 2.86) 3 parts by mass of sugar ester compound of formula (I) 1 part by mass of sugar ester compound of formula (II) silica Particle dispersion (average particle size: 16 nm) “AEROSIL R972”, manufactured by Nippon Aerosil Co., Ltd. 0.026 parts by mass ・ Methylene chloride 377 parts by mass ・ Methanol 61 parts by mass ・ Butanol 2.6 parts by mass

Formula (I)

Formula (II)

(Preparation of cellulose acylate solution for drum layer)
The following composition was put into a mixing tank and stirred while heating to dissolve each component, thereby preparing a cellulose acylate solution for a drum layer.

Composition of Cellulose Acylate Solution for Drum Layer 100 parts by mass of cellulose acylate (acetyl substitution degree 2.86) 3 parts by mass of sugar ester compound of formula (I) 1 part by mass of sugar ester compound of formula (II) silica Particle dispersion (average particle size: 16 nm) “AEROSIL R972”, manufactured by Nippon Aerosil Co., Ltd. 0.091 parts by mass ・ Methylene chloride 339 parts by mass ・ Methanol 74 parts by mass ・ Butanol 3 parts by mass

(Preparation of cellulose acylate solution for core layer)
The following composition was put into a mixing tank, and stirred while heating to dissolve each component to prepare a cellulose acylate solution for a core layer.

Composition of cellulose acylate solution for core layer: 100 parts by mass of cellulose acylate (acetyl substitution degree 2.86) 8.3 parts by mass of sugar ester compound of formula (I) 2.8 sugar ester compound of formula (II) Parts by mass-266 parts by mass of methylene chloride-58 parts by mass of methanol-2.6 parts by mass of butanol

(Film formation by co-casting)
As the casting die, an apparatus equipped with a feed block adjusted for co-casting and capable of forming a three-layer film was used. The cellulose acylate solution for the air layer, the cellulose acylate solution for the core layer, and the cellulose acylate solution for the drum layer were co-cast on a drum cooled to −7 ° C. from a casting port. At this time, the flow rate of each dope was adjusted so that the thickness ratio was air layer / core layer / drum layer = 7/90/3.
The film was cast on a mirror-finished stainless steel support having a diameter of 3 m. Dry air at 34 ° C. was blown on the drum at 300 m ³ / min.
The cellulose acylate film that had been cast and rotated was peeled off from the drum 50 cm before the end point of the casting section, and then both ends were gripped with a pin tenter. At the time of peeling, 8% stretching was performed in the transport direction (longitudinal direction).

The cellulose acylate web held by the pin tenter was conveyed to the drying zone. In the first drying, a drying air at 45 ° C. was blown, and then drying was performed at 110 ° C. for 5 minutes. At this time, the cellulose acylate web was conveyed while being stretched in the width direction at a magnification of 10%.
After separating the web from the pin tenter, the portion held by the pin tenter was continuously cut off, and irregularities having a width of 15 mm and a height of 10 μm were formed on both ends in the width direction of the web. At this time, the width of the web was 1610 mm. It was dried at 140 ° C. for 10 minutes while applying a tension of 130 N in the transport direction. Furthermore, the width direction end was continuously cut so that the web had a desired width, and a substrate 1 having a film thickness of 60 μm was produced. At this time, the film thickness at the edge in the width direction cut off after drying at 140 ° C. and the film thickness at the center of the web were the same.

  FUJITAC TG60UL is a cellulose acylate film manufactured by FUJIFILM Corporation.

(Preparation of substrate with hard coat layer)
<Formation of Hard Coat Layer A, Hard Coat Layer B, and Hard Coat Layer C>
A coating solution for forming a hard coat layer A or a coating solution for forming a hard coat layer B having the following composition is applied onto FUJITAC TG60UL, and while adjusting to an oxygen concentration of 1.0% by volume with a nitrogen purge, an air-cooled metal halide lamp is used. The coating was cured by irradiating an ultraviolet ray having an irradiation amount of 20 mJ / cm ² to form a hard coat layer A or a hard coat layer B having a thickness of 8 μm.

The substrate with a hard coat layer used for Sample 102 was prepared by applying a coating solution for forming a hard coat layer C having the following composition on the substrate 1 and adjusting the oxygen concentration to 1.0% by volume with nitrogen purge. The hard coat layer C having a thickness of 8 μm was formed by irradiating an ultraviolet ray with an irradiation amount of 1000 mJ / cm ^{2 using} an air-cooled metal halide lamp to cure the film.

(Composition of the coating solution for forming the hard coat layer A)
UNIDIC 17-806 55.8 parts by mass Irgacure 127 1.9 parts by mass Methyl ethyl ketone 24.5 parts by mass Methyl isobutyl ketone 8.9 parts by mass 8.9 parts by mass methyl acetate

(Composition of the coating solution for forming the hard coat layer B)
UNIDIC17-806 55.8 parts by mass Irgacure 127 1.9 parts by mass Methyl ethyl ketone 24.5 parts by mass Methyl acetate 17.8 parts by mass

(Composition of the coating solution for forming the hard coat layer C)
PET-30 33.4 parts by mass VF-096 1.4 parts by mass Irgacure 127 0.2 parts by mass Methyl ethyl ketone 35.8 parts by mass Methyl acetate 29.3 parts by mass

UNIDIC17-806: urethane acrylate (manufactured by DIC Corporation, 80% solid content solution)
PET-30: a mixture of 60% pentaeristol triacrylate and 40% pentaeristol tetraacrylate (KAYARAD PET-30 (manufactured by Nippon Kayaku Co., Ltd.))
Irgacure 127: Photopolymerization initiator (BASF Japan)
VF-096: 2,2'-azobis [N- (2-propenyl) -2-methylpropionamide]: thermal polymerization initiator

(Preparation of coating liquid for forming antireflection layer Aa1)
Each component was put into a mixing tank so as to have the composition of the antireflection layer Aa1 described below, stirred for 60 minutes, dispersed by an ultrasonic disperser for 30 minutes, and filtered through a polypropylene filter having a pore diameter of 5 μm to form an antireflection layer. A coating solution was used.

(Composition of coating liquid for forming antireflection layer Aa1)
Sirius-501 2.5 parts by mass Compound B 3.9 parts by mass KBM-4803 4.5 parts by mass Ethanol 15.3 parts by mass Methyl ethyl ketone 32.2 parts by mass Acetone 15.3 parts by mass Irgacure 127 0.4 parts by mass Silica particles Dispersion α 25.9 parts by mass Compound D 0.08 parts by mass

  Compound D in the coating liquid for forming the antireflection layer Ab1 is a fluorine-containing polymer, which is a slipping agent (a), and Sirius-501, compound B, and KBM-4803 are curable compounds (b), and are Irgacure. 127 is a photopolymerization initiator (c), the silica particles in the silica particle dispersion α are particles (d), and ethanol, methyl ethyl ketone, and acetone are solvents.

  In the same manner as in the preparation of the coating solution for forming the antireflection layer Aa1, instead of the fluoropolymer compound D as the slipping agent (a) and the curable compound (b), the slipping agent (a) shown in Table 1 and curing were used. A coating liquid for forming the antireflection layers Aa2, Aa4, and Aa5 was prepared using the reactive compound (b). The coating liquid for forming the antireflection layer Aa3 was prepared in the same manner as for Aa4, except that U-15HA was used instead of Sirus-501 and KBM-4803 as the curable compound (b).

(Preparation of coating liquid for forming antireflection layer Ab1)
Each component was put into a mixing tank so as to have the composition of the following antireflection layer Ab1, stirred for 60 minutes, dispersed by an ultrasonic disperser for 30 minutes, and filtered through a polypropylene filter having a pore size of 5 μm to form an antireflection layer. A coating solution was used.

(Composition of coating liquid for forming antireflection layer Ab1)
Sirius-501 2.5 parts by mass Compound B 3.9 parts by mass KBM-4803 4.5 parts by mass Ethanol 15.3 parts by mass Methyl ethyl ketone 32.2 parts by mass Acetone 15.3 parts by mass Irgacure 127 0.4 parts by mass Silica particles Dispersion α 25.9 parts by mass P-10 0.08 parts by mass

  In the same manner as in the preparation of the coating liquid for forming the antireflection layer Ab1, the silicone-based polymer P-10 as the slipping agent (a) and the slipping agents (a) shown in Table 1 instead of the curable compound (b) were used. Using the curable compound (b), coating liquids for forming the antireflection layers Ab2 to Ab8 were prepared.

(Preparation of coating liquid for forming antireflection layer Ac1)
Each component was put into a mixing tank so as to have the composition of the following antireflection layer Ac1, stirred for 60 minutes, dispersed by an ultrasonic disperser for 30 minutes, and filtered through a polypropylene filter having a pore size of 5 μm to form an antireflection layer. A coating solution was used.

(Composition of coating liquid for forming antireflection layer Ac1)
Sirius-501 2.5 parts by mass Compound B 3.9 parts by mass KBM-4803 4.5 parts by mass Ethanol 15.3 parts by mass Methyl ethyl ketone 32.2 parts by mass Acetone 15.3 parts by mass Irgacure 127 0.4 parts by mass Silica particles Dispersion α 25.9 parts by mass Compound S-1 0.12 parts by mass

  In the same manner as in the preparation of the coating liquid for forming the antireflection layer Ac1, the silicone-based monomer compound S-1 as the slipping agent (a) and the slipping agent (a) shown in Table 1 in place of the curable compound (b) Using the curable compound (b), a coating liquid for forming the antireflection layers Ac2 to Ac20 was prepared.

Compound B: acrylic group-containing trimethoxysilane represented by the following formula (10) (manufactured by Shin-Etsu Chemical Co., Ltd.)
Equation (10)

  Compound C: a solution of a fluorine-containing polymer SP-13 (weight average molecular weight 19000) having the following structure in a methyl ethyl ketone (MEK) solution having a solid content of 40% by mass.

Compound D: MEK solution of a fluorine-containing polymer (weight average molecular weight 11,000) having a structure represented by the following formula (12) at a solid content concentration of 40% by mass Formula (12)

Compound E: MEK solution of a fluorine-containing polymer having a structure represented by the following formula (13) (weight average molecular weight: 17000) at a solid content concentration of 40% by mass Formula (13)

Compound F: MEK solution of a fluorine-containing polymer having a structure represented by the following formula (14) (weight average molecular weight 11,000) having a solid content concentration of 40% by mass Formula (14)

<Synthesis of silicone polymer (P-10)>
Polydimethylsiloxane-terminated monomer (MCR-M11, manufactured by Gelest) (0.2 mol), allyl methacrylate (0.8 mol), and 2,2′-azobis (2 -Methylbutyronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.) (0.05 mol) in 1-methoxy-2-propanol (300 g) was treated with 1-methoxy-2-propanol at 80 ° C. under a nitrogen stream. It was added dropwise to propanol (300 g) over 4 hours. After completion of the dropwise addition, the mixture was further stirred at 85 ° C for 3 hours to obtain a polymer (P-10). The weight average molecular weight of this polymer (P-10) was 19,000 as measured by gel permeation chromatography. Further, the structure of the obtained polymer (P-10) was identified by nuclear magnetic resonance (NMR).

  A silicone polymer (P-11) having the following structure was synthesized in the same manner as described above.

<Synthesis of silicone polymer (P-12)>
Monomer (MCR-M11, manufactured by Gelest) having a polydimethylsiloxane terminal modified with a methacryloxypropyl group (0.1 mol), compound (M-1) having the following structure (0.9 mol), and 2,2 A 1-methoxy-2-propanol (300 g) solution of '-azobis (2-methylbutyronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.) (0.05 mol) was added at 80 ° C. in a nitrogen stream at 80 ° C. -Methoxy-2-propanol (300 g) was added dropwise over 4 hours. After completion of the dropwise addition, the mixture was further stirred at 85 ° C. for 3 hours to obtain a 1-methoxy-2-propanol solution of the precursor (Q-12) of the polymer (P-12).

  The obtained 1-methoxy-2-propanol solution of (Q-12) was cooled to 0 ° C, and 4,4-dimethylaminopyridine (0.8 mol) was added dropwise over 1 hour. C) and reacted at room temperature for 2 hours to obtain a silicone-based polymer (P-12). The weight average molecular weight of this polymer (P-12) measured by gel permeation chromatography was 14,000. Further, the structure of the obtained polymer (P-12) was identified by NMR. In the following equation, n ≒ 8.

  Silicone polymers (P-13) and (P-14) were synthesized in the same manner as above.

<Compounds (S-1) to (S-8)>
Compounds (S-1) to (S-8) are the compounds described as specific examples of the aforementioned general formulas (4) to (7).

<Silicone monomer (S-9)>
In the above general formula (4), n is 10, R ⁴¹ is —CONH (CH ₂ ) ₃ —, and R ⁴² is —CH ₃ .
(S-9)

<Silicone monomer (S-10)>
In the above formula (5), n is 10, R ⁵¹ is —CONH (CH ₂ ) ₃ —, and R ⁵² is —CH ₃ .

  (S-10)

<Silicone monomer (S-11)>
In the above general formula (6), the compound is one wherein n is 10 and R ⁶¹ and R ⁶² are —CONH (CH ₂ ) ₃ —.

  (S-11)

<Silicone monomer (S-12)>
In the above general formula (7), the compound is one wherein n is 10 and R ⁷¹ and R ⁷² are —CONH (CH ₂ ) ₃ —.

  (S-12)

<Silicone monomer>
Compound (S-13): a compound of the formula (4), wherein n is 4, R ⁴¹ is — (CH ₂ ) ₃ —, and R ⁴² is —CH ₃ .
Compound (S-14): In the general formula (4), n is 160, R ⁴¹ is — (CH ₂ ) ₃ —, and R ⁴² is —CH ₃ .
Compound (S-15): a compound of the formula (6), wherein n is 2 and R ⁶¹ and R ⁶² are — (CH ₂ ) ₃ —.
Compound (S-16): a compound of the formula (6), wherein n is 102 and R ⁶¹ and R ⁶² are — (CH ₂ ) ₃ —.

  The silica particle dispersions α, β, and γ were each prepared by the following methods.

(Preparation of silica particle dispersion α)
KE-P20 was calcined at 1050 ° C. for 1 hour using an electric furnace, cooled, and then pulverized using a pulverizer. 5 kg of the fired KE-P20 was charged into a 20 L Henschel mixer (Model FM20J manufactured by Mitsui Mining Co., Ltd.) equipped with a heating jacket. While the fired KE-P20 was being stirred, a solution in which 45 g of 3-acryloxypropyltrimethoxysilane (KBM5103 manufactured by Shin-Etsu Chemical Co., Ltd.) was dissolved in 90 g of methyl alcohol was dropped and mixed. Thereafter, the temperature was raised to 150 ° C. over about 1 hour while mixing and stirring, and the heat treatment was performed by holding at 150 ° C. for 12 hours, and the scraping device was constantly rotated in the opposite direction to the stirring blade. Then, the deposits on the wall were scraped off. In addition, the material adhering to the wall surface was scraped off using a spatula as appropriate. After heating, the mixture was cooled, crushed and classified using a jet pulverizing classifier to obtain particles surface-treated with a silane coupling agent. An acryloyl group is provided on the surface of the particle.
80 parts by mass of MEK and 20 parts by mass of the above silica particles are put into a mixing tank, stirred for 10 minutes, and then ultrasonically dispersed for 30 minutes while stirring is continued to prepare a silica particle dispersion α having a solid concentration of 20% by mass. did.
The average primary particle size of the silica particles contained in the silica particle dispersion liquid α is 180 nm.

(Preparation of silica particle dispersion β)
KE-P30 was calcined at 1050 ° C. for 1 hour using an electric furnace, cooled, and then pulverized using a pulverizer. 5 kg of the calcined KE-P30 was charged into a 20 L Henschel mixer (model FM20J manufactured by Mitsui Mining Co., Ltd.) equipped with a heating jacket. While the fired KE-P30 was being stirred, a solution in which 30 g of 3-acryloxypropyltrimethoxysilane (KBM5103 manufactured by Shin-Etsu Chemical Co., Ltd.) was dissolved in 90 g of methyl alcohol was dropped and mixed. Thereafter, the temperature was raised to 150 ° C. over about 1 hour with mixing and stirring, and the heat treatment was performed by holding at 150 ° C. for 12 hours, and the scraping device was constantly rotated in the opposite direction to the stirring blade. Then, the deposits on the wall were scraped off. In addition, the material adhering to the wall surface was scraped off using a spatula as appropriate. After heating, the mixture was cooled, crushed and classified using a jet pulverizing classifier, to obtain particles surface-treated with a silane coupling agent. An acryloyl group is provided on the surface of the particle.
80 parts by mass of MEK and 20 parts by mass of the above silica particles are put into a mixing tank, and after stirring for 10 minutes, ultrasonic dispersion is performed for 30 minutes while stirring is continued to prepare a silica particle dispersion β having a solid content concentration of 20% by mass. did.
The average primary particle size of the silica particles contained in the silica particle dispersion β is 270 nm.

(Preparation of silica particle dispersion γ)
PL-7 (manufactured by Fuso Chemical Co., Ltd.) was calcined at 1050 ° C. for 1 hour using an electric furnace, cooled, and then pulverized using a pulverizer. 55 kg of the baked PL-75 was charged into a 20 L Henschel mixer (Model FM20J manufactured by Mitsui Mining Co., Ltd.) equipped with a heating jacket. While the calcined PL-7 was being stirred, a solution prepared by dissolving 65 g of 3-acryloxypropyltrimethoxysilane (KBM5103 manufactured by Shin-Etsu Chemical Co., Ltd.) in 90 g of methyl alcohol was dropped and mixed. Thereafter, the temperature was raised to 150 ° C. over about 1 hour while mixing and stirring, and the heat treatment was performed by holding at 150 ° C. for 12 hours, and the scraping device was constantly rotated in the opposite direction to the stirring blade. Then, the deposits on the wall were scraped off. In addition, the material adhering to the wall surface was scraped off using a spatula as appropriate. After heating, the mixture was cooled, crushed and classified using a jet pulverizing classifier to obtain particles surface-treated with a silane coupling agent. An acryloyl group is provided on the surface of the particle.
80 parts by mass of MEK and 20 parts by mass of the above silica particles are put into a mixing tank, and after stirring for 10 minutes, ultrasonic dispersion is performed for 30 minutes while stirring is continued to prepare a silica particle dispersion γ having a solid concentration of 20% by mass. did.
The average primary particle size of the silica particles contained in the silica particle dispersion liquid γ is 90 nm.

U-15HA: urethane acrylate (acryl equivalent: 139, manufactured by Shin-Nakamura Chemical Co., Ltd.)
X-12-1048: acrylic group-containing trimethoxysilane (acryl equivalent: 370, manufactured by Shin-Etsu Chemical Co., Ltd.)
Sirius-501: Dendrimer type polyfunctional acrylate (acryl equivalent: 110, manufactured by Osaka Organic Chemical Industry Co., Ltd.)
KBM-4803: glycidoxyoctyltrimethoxysilane (epoxy equivalent 306, manufactured by Shin-Etsu Chemical Co., Ltd.)
KE-P20: Seahoster KE-P20 (average primary particle size 200 nm, amorphous silica manufactured by Nippon Shokubai Co., Ltd.)
KE-P30: Seahoster KE-P30 (average primary particle size 300 nm, amorphous silica manufactured by Nippon Shokubai Co., Ltd.)
PL-7: Quartron PL-7 ultra-high purity colloidal silica (average primary particle diameter 100 nm, manufactured by Fuso Chemical Industry Co., Ltd.)
8SS-723: Acryt 8SS-723 (crosslinking group equivalent 338, manufactured by Taisei Fine Chemical Co., Ltd.)
8SS-1024: Acryt 8SS-1024 (crosslinking group equivalent 263, manufactured by Taisei Fine Chemical Co., Ltd.)
UMS-182: polymerizable group-containing polydimethylsiloxane (molecular weight 6,500, acryl equivalent 545, manufactured by Gelest Co., Ltd.)
X-22-164C: a polydimethylsiloxane monomer having a methacryloyl group at both ends (molecular weight 4800, acryl equivalent 2400, manufactured by Shin-Etsu Chemical Co., Ltd.)
X-22-164: a polydimethylsiloxane monomer having a methacryloyl group at both ends (molecular weight: 380, acryl equivalent: 190, manufactured by Shin-Etsu Chemical Co., Ltd.)

  Antireflection film samples 1 to 23 and 101 to 111 were produced by the following steps (1) to (4).

[Step (1) Application of coating liquid for forming antireflection layer]
2.8 ml / m ^{2 of an} antireflection layer forming coating solution was applied to the hard coat layer of the substrate having a hard coat layer using a die coater, and dried at room temperature for 90 seconds.
A portion of the sample was cut out, irradiated with an air-cooled metal halide lamp at 600 mJ / cm ² , cured, then cut with a microtome to obtain a cross section, and subjected to SEM observation at 5,000 times to measure the thickness of the resin relative to the particles. In all Examples and Comparative Examples, the thickness of the resin in the portion where no particles were present was 0.8 times or more the average primary particle size of the particles.

[Step (2)]
In step (2), a sample having a curing rate of 6% was prepared by irradiating 2.0 mJ / cm ² from the antireflection layer side using an air-cooled metal halide lamp in an environment with an oxygen concentration of 1.0%. M04-L41 manufactured by Eye Graphics Co., Ltd. was used as an air-cooled metal halide lamp.
The measurement of the irradiation amount was performed by attaching HEAD SENSER PD-365 to an eye ultraviolet integrating illuminometer UV METER UVPF-A1 manufactured by Eye Graphic Co., Ltd., and measuring it at a measurement range of 0.0.
For sample 102, light irradiation was performed from the side opposite to the interface on the antireflection layer side of the substrate.

(Oil application)
An oil solution having the following composition (all silicone oils manufactured by Shin-Etsu Chemical Co., Ltd.) was applied on the antireflection layer using a die coater to a thickness of 600 nm.
Composition of oil liquid KF96-10cs 30.0 parts by mass KF96-0.65cs 70.0 parts by mass

[Step (3)]
The laminated body having the substrate, the hard coat layer, and the antireflection layer after the step (2) was treated at 120 ° C. for 5 minutes to allow a part of the curable compound to permeate the substrate.

[Step (4)]
The above-mentioned air-cooled metal halide lamp was irradiated with ultraviolet rays of 600 mJ / cm ² while purging with nitrogen so that the oxygen concentration became 0.01% by volume or less to cure the curable compound of the antireflection layer and the resin. did.
A part of the sample was cut out, cut with a microtome to obtain a cross section, and SEM observation was performed at 5,000 times to measure the thickness of the resin (part where no particles exist) with respect to the particles. Compared with the SEM observation image after the step (1), in the step (3), a part of the curable compound penetrates the resin whose thickness is reduced by 0.4 times or more of the average primary particle diameter of the particles. It was determined that it was done.

(Oil removal)
In the case where the oil was applied, the oil was removed by immersing in methyl isobutyl ketone and then circulating methyl isobutyl ketone.

(Heat treatment)
The sample 102 containing the thermal polymerization initiator in the composition for forming a hard coat layer was subjected to a heat treatment at 150 ° C. for 5 minutes after the step (4) to cure the hard coat layer.

[Steel wool resistance (scratch resistance test)]
The surface of the anti-reflection layer of the anti-reflection film was subjected to a rubbing test using a rubbing tester under the following conditions to obtain an index of scratch resistance.
Evaluation environment conditions: 25 ° C, relative humidity 60%
Rubbing material: steel wool (Grade No. 0000, manufactured by Nippon Steel Wool Co., Ltd.)
Wrap around the rubbing tip (1 cm x 1 cm) of the tester in contact with the sample and fix the band. Moving distance (one way): 13 cm,
Rubbing speed: 13 cm / sec,
Load: 200 g / cm ² ,
Tip contact area: 1cm × 1cm,
Number of rubs: 10 reciprocations Oily black ink (manufactured by Teranishi Kagaku Kogyo Co., Ltd., magic refill ink black) was applied to the back side of the rubbed sample, and the scratches on the rubbed portion were evaluated by visual observation with reflected light.
A +: The number of scratches is 0 A: The number of scratches is 1 or more and 2 or less B: The number of scratches is 3 or more and 5 or less C: The number of scratches is 6 or more

[Specular reflectance]
The back surface (substrate side) of the antireflection film was roughened with sandpaper and then treated with oily black ink to prepare a film sample in which the back surface reflection was eliminated.
(Mirror reflectance)
A unit ARM-500∨ was attached to a spectrophotometer V-550 (manufactured by JASCO Corporation), and the reflectance at an incident angle of 5 ° was measured in a wavelength region of 450 to 650 nm, and the average was mirror reflectance. And
(Specular reflectance difference before and after steel wool abrasion resistance test)
The reflectance change represented by (R _A -R ₀ ) was calculated assuming that the mirror reflectance after the steel wool scratch resistance test was _RA and the mirror reflectance before rubbing with steel wool was R ₀ .

[Content of low friction site of slip agent (a)]
The film was cut with a microtome, and the cross section was analyzed with a time-of-flight secondary ion mass spectrometer (TOF-SIMS) to observe the state from the outermost surface to a depth of 20 nm (near the surface). X is the amount of fluorine or silicone (siloxane bond) in the vicinity of the surface of the antireflection layer, and Y is 100 * (X / Y) when the amount of fluorine in the single film of the slipping agent (a) or the amount of silicone (siloxane bond) is used. ) Was calculated. The secondary ions representing a low friction portion of the slip agent (a) F ^- was detected fragments or _Si 2 _C 5 _H 15 ^{O +} fragment.

  From the results shown in Table 2, the sample containing a large amount of the slip agent (a) having a small acrylic equivalent and a high crosslinking density in the vicinity of the surface of the antireflection layer opposite to the substrate in the antireflection layer has a low reflectance and a high steel resistance. It was confirmed that the wool rubbing was good, the reflectance increase after rubbing steel wool was small, and the scratch resistance in practical use was excellent.

Sample No. 13 and 22 were subjected to the following saponification treatment. A 1.5 mol / l sodium hydroxide aqueous solution was prepared and kept at 55 ° C. A 0.01 mol / l dilute sulfuric acid aqueous solution was prepared and kept at 35 ° C. The prepared optical film was immersed in the above-described aqueous sodium hydroxide solution for 2 minutes, and then immersed in water to sufficiently wash away the aqueous sodium hydroxide solution. Next, after immersing in the above-mentioned diluted sulfuric acid aqueous solution for 1 minute, it was immersed in water and the diluted sulfuric acid aqueous solution was sufficiently washed away. Finally, the sample was thoroughly dried at 120 ° C.
Sample No. Sample No. 13 maintained steel wool resistance A + even after saponification treatment and was good. No. 22 confirmed that the steel wool resistance was deteriorated to A.

  According to the present invention, it is possible to provide a practical anti-reflection film having excellent anti-reflection performance, a small change in reflectance before and after a scratch resistance test, and excellent practical scratch resistance. It is possible to propose a method capable of easily producing a film.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on Japanese Patent Application (No. 2006-033786) filed on Feb. 25, 2016, the contents of which are incorporated herein by reference.

REFERENCE SIGNS LIST 1 base material 2 antireflection layer 3 particles 4 layer (A), resin 10 antireflection film A distance B between vertices of adjacent convex parts Distance S between the center between vertices of adjacent convex parts and concave part S (S)
t Region (S) film thickness

Claims (12)

On the substrate, having at least one antireflection layer,
The antireflection layer has a thickness (S) of 20 nm or less in a direction from the outermost surface opposite to the surface on the base material side toward the base material,
A slip agent (a) having three or more cross-linking groups in one molecule, having a cross-linking group equivalent of 450 or less, and having a site containing at least one of a fluorine atom and a siloxane bond;
A curable compound (b) having at least three crosslinking groups in one molecule, having a crosslinking group equivalent of 450 or less, and having neither a fluorine atom nor a siloxane bond;
A photopolymerization initiator (c), and a cured product of a curable composition containing:
The compound (a1) having a site containing at least one of the fluorine atom and the siloxane bond in a side chain and the crosslinking group, and having a weight average molecular weight of 6,000 or more, or the fluorine atom (a). And a compound (a2) having a weight-average molecular weight of less than 6,000, wherein the cross-linking group is bonded directly or via a linking group to a site containing at least one siloxane bond,
The site of the compound (a1) containing at least one of the fluorine atom and the siloxane bond is a site containing at least one of a fluoroalkyl group and a siloxane bond represented by the following general formula (P);
The site containing at least one of the fluorine atom and the siloxane bond of the compound (a2) is a site containing a siloxane bond represented by the following general formula (P),
The compound (a2) is
A compound having one group represented by the following general formula (M-2),
A compound having one group represented by the following general formula (M-3),
A compound having two groups represented by the following general formula (M-1),
A compound having two groups represented by the following general formula (M-2), or
A compound having two groups represented by the following general formula (M-3),
An antireflection film having a region in which a content of the slip agent (a) is 51% or more in a material distribution in a cross-sectional direction of the region (S).

In formula (P), Rp ¹ and Rp ² each independently represent a hydrogen atom, a monovalent hydrocarbon group, an alkoxy group, or an aryloxy group. n represents an integer of 2 or more.

In Formula (M-1), R ₁ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkyloxy group, an alkenyloxy group, an alkyloxyalkyl group, or an alkenyloxyalkyl group. R ₁₁ and R ₁₂ each independently represent a hydrogen atom or a methyl group. * Represents a bonding position.
In Formula (M-2), R _{21 to} R ₂₃ each independently represent a hydrogen atom or a methyl group. * Represents a bonding position.
In Formula (M-3), R _{31 to} R ₃₅ each independently represent a hydrogen atom or a methyl group. * Represents a bonding position. The reflectivity of the antireflection film after rubbing the outermost surface of the antireflection layer opposite to the surface on the substrate side with steel wool 10 times under the condition of a load of 200 g is R _A , before rubbing with steel wool. wherein when the reflectance of the antireflection film was R ₀ of change in reflectance represented by R _a -R ₀ it is not more than 0.25%, the anti-reflection film of claim 1.   The antireflection film according to claim 1, wherein the crosslinking group of the slip agent (a) is a (meth) acryloyl group.   The antireflection according to any one of claims 1 to 3, wherein the portion of the slip agent (a) containing at least one of the fluorine atom and the siloxane bond is a polydimethylsiloxane group or a polyether-modified dimethylsiloxane group. the film. A said slip agent (a) is the compound (a1), the compound (a1), the bridging group is linked to the main chain at C-C bond or C-O bonds, claims 1 to 4 The antireflection film according to any one of the above. The slipping agent (a) is the compound (a2), and the compound (a2) is a compound containing at least one of the fluorine atom and the siloxane bond, and the crosslinking group having a CC bond or a CO bond. The antireflection film according to claim 1, wherein the antireflection film is bonded via a bond. The antireflection film according to any one of claims 1 to 6 , wherein the antireflection layer has particles (d) having an average primary particle size of 250 nm or less. The anti-reflection film according to claim 7 , wherein the anti-reflection film has an uneven shape formed by the particles (d) on a surface of the anti-reflection layer opposite to the substrate side. The antireflection film according to any one of claims 1 to 8 , wherein the base material has a visible light transmittance of 80% or more. The anti-reflection film according to claim 8 , wherein the anti-reflection layer does not include a plurality of the particles (d) in a direction orthogonal to a surface of the substrate. It is a manufacturing method of the antireflection film of Claim 8 , Comprising:
On the substrate,
A composition containing the slip agent (a), the curable compound (b), the photopolymerization initiator (c), the particles (d), and a solvent is applied, the solvent is volatilized, and the particles (d (1) providing a layer (A) in which the thickness of the portion where no) is present is at least 0.8 times the average primary particle size of the particles (d);
A step (2) of curing a part of the curable compound (b) in the layer (A) to obtain a cured compound (bc);
Part of the compound selected from the group consisting of the curable compound (b) and the compound (bc) in the layer (A) is made to penetrate or volatilize the base material by heating, and the layer (A) (3) forming an uneven shape composed of the particles (d) on the outermost surface opposite to the substrate side;
The anti-reflection layer is formed by curing a compound selected from the group consisting of the slip agent (a), the curable compound (b) and the compound (bc) remaining in the layer (A). Step (4),
In this order, the method for producing an antireflection film. Between the step (1) and the step (2), between the step (2) and the step (3), or between the step (3) and the step (4);
A step (E1) of providing a layer (E) containing a compound (e) incompatible with the curable compound (b) on the surface of the layer (A) opposite to the surface on the substrate side. Have
The method according to claim 11 , further comprising a step (E2) of removing the layer (E) after the step (2), the step (3), or the step (4) performed subsequent to the step (E1). Manufacturing method of antireflection film.

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